Palladium-catalyzed construction of axially chiral allenol derivatives from allenyl dimethylene cyclic carbonates and their applications

Abstract

The present invention discloses a palladium-catalyzed novel allenyl dimethylene cyclic carbonate for the construction of axially chiral allenol derivatives and their applications. The present invention designs and synthesizes a novel class of allenyl dimethylene cyclic carbonate (ACCs) substrates. Under palladium catalysis, these substrates undergo ring-opening decarboxylation and desymmetrization to form novel allyl palladium zwitterions. These zwitterions then undergo asymmetric desymmetrization allylation reactions with various nucleophiles (including sodium arylsulfinates, 2-pyridones, heteroaromatic nucleophiles, secondary amines, and bis(benzenesulfonic acid) methane). This allows for the efficient and highly enantioselective construction of a series of trisubstituted axially chiral allenol derivatives with potential biological, fluorescent, or catalytic activity under mild reaction conditions, providing new strategies and methods for the rapid and efficient synthesis of axially chiral allene compounds.

Description

Technical Field

[0001] The invention belongs to the field of asymmetric synthesis in organic chemistry, and particularly relates to a palladium-catalyzed novel allenyl dimethylene cyclic carbonate for constructing an axially chiral allenol derivative and application thereof. Background Art

[0002] The information disclosed in this background technology section is only intended to enhance some understanding of the overall background of the invention and should not be necessarily regarded as an admission or any form of suggestion that the information constitutes the prior art already known to those skilled in the art.

[0003] The unique presence of two cumulative carbon-carbon double bonds in the allene structure allows the substitution of hydrogen atoms to form a unique axially chiral stereoconfiguration. This property makes allene compounds uniquely reactive in organic synthesis, allowing them to participate in a wide range of chemical reactions to yield multiply substituted axially chiral allene products. Furthermore, axially chiral allene skeletons are widely found in biologically active natural products and pharmaceuticals, such as malacin, which exhibits antifungal activity; neolutein, which induces apoptosis and has anticancer activities; locustin, which exhibits antioxidant and anti-inflammatory activities; citrate glycosides; carbacycline derivatives with antitumor activity; allene nucleosides with nucleosidase inhibitory activity; and the anti-ulcer drug enprostil. Studies have shown that the introduction of an axially chiral allene structure can significantly alter the electron distribution and spatial configuration of the molecule, thereby modifying the compound's original pharmacological and biological activities. Therefore, the development of novel synthetic methods for axially chiral allene compounds is not only of great theoretical significance but also holds broad application prospects in drug discovery and functional material development.

[0004] To date, transition metal-catalyzed asymmetric allenyl substitution is one of the most direct and efficient methods for synthesizing chiral allene compounds with high optical purity. However, compared with the asymmetric allylic / propargyl substitution reaction with similar reaction process, there are relatively few successful examples of asymmetric allenyl substitution reaction. In 2002, Imada's group reported the zero-valent palladium-catalyzed asymmetric allenylation reaction of allenyl phosphate with dimethyl malonate or substituted diethyl malonate. N , O -Bistrimethylsilyl acetamide (BSA) is a base, ( R )-(+)-(6,6'-dimethoxybiphenyl-2,2'-yl)bis(diphenylphosphine) as ligand, chiral allene products can be obtained with moderate to excellent enantioselectivity. R )-5,5'-bis(diphenylphosphoryl)-4,4'-di-1,3-biphenyl or ( RUsing )-(-)-5,5'-bis[di(3,5-di-tert-butyl-4-methoxyphenyl)phosphine]-4,4'-di-1,3-benzodioxolane as a ligand, the nucleophile class was further expanded to include primary and secondary amines. Starting from primary amines, bis-alkenyl-substituted tertiary amines were obtained, although with poor diastereoselectivity. Starting from secondary amines, the corresponding axially chiral allenyl tertiary amines were obtained. In 2005, the Trost group used their own ligand to achieve a palladium-catalyzed asymmetric allenylation of allenyl acetates with malonates and secondary amines. The substituents in the allenyl acetates must be sterically hindered to achieve good ee values. In 2009, the Hamada group used a chiral diaminophosphite generated in situ in the reaction system of diaminophosphine oxide and BSA as a ligand to achieve a similar asymmetric allenylation reaction. Subsequently, the Aso Akira group achieved excellent enantioselectivity for optically active allenes containing one axial chirality through palladium-catalyzed asymmetric intramolecular decarboxylative alleneation of allenyl carbamates. In 2012, they achieved palladium-catalyzed asymmetric alleneation of allenyl acetates with diethyl malonate to obtain allene compounds containing one central chirality. In 2014, their group further expanded the substrate scope of the reaction to include secondary p-toluenesulfonylamine. In 2019, the Trost group used α-hydroxyketones as nucleophile precursors and, with the assistance of boron reagents, asymmetric allene substitution reactions with racemic allyl acetates to obtain axially chiral allene products with good selectivity. Then, in 2023, the Shao Zhihui group used indole as a nucleophile and a similar strategy to achieve regioselective asymmetric allylic substitution reactions at the N1- and C3-positions of indoles. In the same year, their research group used allene compounds with double leaving groups to carry out asymmetric allene substitution reaction with amine compounds under palladium catalysis to construct axial chiral allenes.

[0005] In summary, it is not difficult to find that the currently known palladium-catalyzed asymmetric allenyl substitution reactions mainly revolve around the formation of η by racemic allene compounds containing leaving groups under palladium catalysis. 3 Asymmetric allenyl substitution reactions involving π-allylpalladium intermediates with various nucleophiles typically require additional bases as additives. However, asymmetric allenyl substitution reactions involving π-allylpalladium zwitterions have not been reported. Summary of the Invention

[0006] Transition metal-catalyzed asymmetric allenyl substitution is one of the most direct and efficient methods for synthesizing chiral allene compounds with high optical purity. However, compared with the asymmetric allylic / propargyl substitution reaction, which has a similar reaction process, there are relatively few successful examples of asymmetric allenyl substitution. In addition, the currently known palladium-catalyzed asymmetric allenyl substitution reactions mainly revolve around the formation of η-terminated allene compounds containing a leaving group under palladium catalysis. 3 Asymmetric allenyl substitution reactions involving π-allylpalladium intermediates with various nucleophiles typically require additional bases as additives. However, asymmetric allenyl substitution reactions involving π-allylpalladium zwitterions have not been reported. This is due to the lack of a novel allenylpalladium zwitterion intermediate in this field. Therefore, we developed a new class of allenyl dimethylene cyclic carbonates (ACCs) as substrates. These substrates undergo palladium-catalyzed ring-opening decarboxylation and desymmetrization to form novel allenylpalladium zwitterions, which can serve as highly active universal intermediates in asymmetric allenyl substitution reactions, leading to the construction of a series of axially chiral allene compounds. The present invention designs and synthesizes a new class of allenyl dimethylene cyclic carbonate (ACCs) substrates. Under palladium catalysis, they can form new allyl palladium zwitterions through ring-opening decarboxylation and desymmetrization. Then, they react with various types of nucleophiles (including sodium arylsulfinate, 2-pyridone, aromatic heterocyclic nucleophiles, secondary amines, and bisbenzenesulfonic acid methane, etc.) to undergo asymmetric desymmetrization and allylation reactions. Under mild reaction conditions, a series of trisubstituted axial chiral allenol derivatives with potential biological activity, fluorescence activity, or catalytic activity can be constructed with high efficiency and high enantioselectivity, such as Figure 1 , providing new strategies and methods for the rapid and efficient synthesis of axially chiral allene compounds.

[0007] The technical solution adopted in the present invention is as follows:

[0008] In the first aspect of the present invention, there is provided an allenyl dimethylene cyclic carbonate compound, the general structural formula of which is shown in I:

[0009] In Formula I, R is selected from Ph, 3-FC6H4, 4-FC6H4, 3-ClC6H4, 4-ClC6H4, 2-MeC6H4, 3-MeC6H4, 4-MeC6H4, 2-MeOC6H4, 3-MeOC6H4, 4-MeOC6H4, 4-PhC6H4, cyclohexyl, and 2-nap. Me represents methyl, Ph represents phenyl, F represents fluorine, Cl represents chlorine, MeO represents methoxy, cyclohexyl represents cyclohexyl, nap represents naphthyl, and black dots represent the middle carbon of the allene structure.

[0010] In a second aspect of the present invention, a method for preparing the allenyl dimethylene cyclic carbonate compound is provided, the method comprising the following steps:

[0011] Under an argon atmosphere, tetrakis(triphenylphosphine)palladium and zinc bromide were dissolved in tetrahydrofuran, and then a Grignard reagent solution was added to react to obtain a crude product of 5-ethynyl-2,2-dimethyl-1,3-dioxane-5-acetate;

[0012] The crude product of 5-ethynyl-2,2-dimethyl-1,3-dioxane-5-acetate was dissolved in methanol, and concentrated sulfuric acid was added dropwise to react to obtain the product of allenedimethylene glycol;

[0013] The allenyl dimethylene glycol product is dissolved in dichloromethane, and triethylamine is added dropwise to react; triphosgene is dissolved in dichloromethane and then added dropwise to the above reaction system to react, and after the reaction is completed, the allenyl dimethylene carbonate product is separated and purified to obtain the allenyl dimethylene cyclic carbonate compound.

[0014] In one or some embodiments of the present invention, the Grignard reagent is an organometallic compound generated by the reaction of a halogenated hydrocarbon (RX) and metallic magnesium (Mg) in an organic solvent (anhydrous ether or tetrahydrofuran), with the general formula R-Mg-X, wherein R is Ph, 3-FC6H4, 4-FC6H4, 3-ClC6H4, 4-ClC6H4, 2-MeC6H4, 3-MeC6H4, 4-MeC6H4, 2-MeOC6H4, 3-MeOC6H4, 4-MeOC6H4, 4-PhC6H4, cyclohexyl, 2-nap, and X is Br, Cl, I, etc.

[0015] In a third aspect of the present invention, there is provided a use of the allenyl dimethylene cyclic carbonate compound as an intermediate of a trisubstituted axial chiral allenol derivative.

[0016] In the fourth aspect of the present invention, a trisubstituted axial chiral allenol derivative is provided, the general structural formula of which is shown in II:

[0017] In Formula II, R is selected from Ph, 3-FC6H4, 4-FC6H4, 3-ClC6H4, 4-ClC6H4, 2-MeC6H4, 3-MeC6H4, 4-MeC6H4, 2-MeOC6H4, 3-MeOC6H4, 4-MeOC6H4, 4-PhC6H4, cyclohexyl, and 2-nap; Nu is selected from substituted 2-pyridone, other nitrogen-containing heterocycles, secondary amines, bisbenzenesulfonate, and substituted sodium arylsulfinate. Nu represents a nucleophile.

[0018] In a fifth aspect of the present invention, a method for preparing the trisubstituted axial chiral allenol derivative is provided, the method comprising the following steps:

[0019] Under an argon atmosphere, an allenyl dimethylene cyclic carbonate compound represented by the general formula (I), a nucleophile, a palladium catalyst, a chiral ligand, and dichloromethane are reacted. After completion of the reaction is monitored by thin-layer chromatography, the resulting axially chiral allene product is purified by flash silica gel column chromatography to obtain a trisubstituted axially chiral allenol derivative.

[0020] In one or some embodiments of the present invention, the nucleophilic reagent is substituted 2-pyridone, other nitrogen-containing heterocycles, secondary amines, bisbenzenesulfonic acid methane, or substituted sodium arylsulfinate.

[0021] Among them, the other nitrogen-containing heterocycles are 2-hydroxypyrazine, 4-hydroxypyrimidine, 3-methyluracil, 1-hydroxyisoquinoline, 4,5-dihydro-4-oxofurano[3,2]pyridine, 4-hydroxythieno[3,2-C]pyridine, substituted 2-hydroxyquinoxaline, isatin, 2-benzoxazolinone, and 2-hydroxybenzothiazole.

[0022] Secondary amines are N -Benzylcyclohexylamine, ( S )-(-)- N -methyl-1-phenylethylamine, N -allylbenzylamine, N -Methylbenzylamine, dibenzylamine, morpholine, benzyl-1-piperazine carbonate.

[0023] In one or some embodiments of the present invention, the chiral ligand is (1R,2R)-(+)-1,2-diaminocyclohexane-N,N'-bis(2-phenylphosphine-1-naphthoyl), N,N'-[(1R,2R)-1,2-diphenyl-1,2-ethanediyl]bis[2-diphenylphosphine benzamide], or N,N'-[(1R,2R)-1,2-bis(2-methoxy)phenyl-1,2-ethanediyl]bis[2-diphenylphosphine benzamide].

[0024] In one or some embodiments of the present invention, the molar ratio of the allenyl dimethylene cyclic carbonate compound represented by the general formula I, the nucleophilic reagent, the palladium catalyst, and the chiral ligand is 1: (0.66~2.5): (0.033~0.05): (0.073~0.11).

[0025] In a sixth aspect of the present invention, there is provided the use of the trisubstituted axial chiral allenol derivative in the synthesis of chiral allen ethers, chiral allen amides, chiral oxygen heterocycles, chiral allenaldehydes, chiral allen ester compounds or as a fluorescent compound.

[0026] Compared with the related art known to the inventors, one of the technical solutions of the present invention has the following beneficial effects:

[0027] The compound of the present invention has a novel structure, a simple preparation process, good substrate universality, a large number of derivatizable compounds, mild reaction conditions, high product yield and good enantioselectivity, and requires a small amount of catalyst.

[0028] The prepared trisubstituted axial chiral allenol derivative has application in synthesizing chiral allen ethers, chiral allenamides, chiral oxygen heterocycles, chiral allenaldehydes, chiral allen ester compounds or as a fluorescent compound. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The accompanying drawings, which constitute a part of the specification of the present invention, are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute improper limitations on the present invention.

[0030] Figure 1 :Palladium-catalyzed asymmetric desymmetric allenyl substitution reaction of novel allenyl dimethylene cyclic carbonates (ACCs) with nucleophiles.

[0031] Figure 2 : Synthetic routes of novel allenyl dimethylene cyclic carbonate compounds with different substitutions.

[0032] Figure 3 : Synthetic route to trisubstituted axially chiral allenols.

[0033] Figure 4 : Optimization of reaction conditions for the preparation of trisubstituted axially chiral allenol derivatives.

[0034] Figure 5 : The synthetic route of the allenyl dimethylene cyclic carbonate compound and 2-pyridone or other nitrogen-containing heterocyclic substrates in Example 2.

[0035] Figure 6 : The synthetic route of the allenyl dimethylene cyclic carbonate compound and the secondary amine substrate in Example 3.

[0036] Figure 7 : The synthetic route of the allenyl dimethylene cyclic carbonate compound and bisbenzenesulfonic acid methane in Example 4.

[0037] Figure 8 : The synthetic route of allenyl dimethylene cyclic carbonate compound and sodium benzenesulfinate in Example 5.

[0038] Figure 9 : The synthetic route for preparing chiral allenol compound 9 from axially chiral allenol product 4aa.

[0039] Figure 10 : The synthetic route for preparing chiral allenamide compound 10 from axially chiral allenol product 4aa.

[0040] Figure 11 : Synthetic route for preparing chiral oxygen heterocyclic compound 11 from axially chiral allenol product 4aa.

[0041] Figure 12 :A synthetic route for preparing iodine-containing chiral oxygen heterocyclic compound 12 from axially chiral allenol product 4aa.

[0042] Figure 13 : The synthetic route for preparing chiral allenal compound 13 from axially chiral allenol product 8ah.

[0043] Figure 14 : The synthetic route for preparing chiral allenol compound 14 from axially chiral allenol product 8ah.

[0044] Figure 15 : The synthetic route for preparing chiral allenol compound 15a from axially chiral allenol product 4aac.

[0045] Figure 16 : The synthetic route for preparing chiral allenol compound 15b from axially chiral allenol product 4aac.

[0046] Figure 17 :A palladium-catalyzed one-pot synthesis route for chiral vinylcyclopropanol derivatives.

[0047] Figure 18 :The synthetic route for preparing 1,3-dienal compound 17 from axially chiral allenol product 6aa.

[0048] Figure 19 :The synthetic route for preparing chiral oxygen heterocyclic compound 18 from axially chiral allenol product 6aa.

[0049] Figure 20 :The synthetic route for preparing chiral allenol compound 19 from axially chiral allenol product 6at.

[0050] Figure 21 :The synthetic route for preparing chiral allenol compound 20 from axially chiral allenol product 6at.

[0051] Figure 22 : Emission spectra of compound 5ai in different solvents. DETAILED DESCRIPTION

[0052] It should be noted that the following detailed descriptions are exemplary and intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the present invention belongs.

[0053] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular form is intended to include the plural form. In addition, it should be understood that when the terms "comprise" and / or "include" are used in this specification, they indicate the presence of features, steps, operations and / or combinations thereof.

[0054] In a typical embodiment of the present invention, a method for preparing a trisubstituted axial chiral allenol derivative is provided, the method comprising the following steps: Figure 3 :

[0055] Under argon, weigh allenyl dimethylene cyclic carbonate compounds, various nucleophiles, 5 mol% palladium catalyst, and 11 mol% chiral ligand into a Shrek tube. Add 1 mL of dichloromethane and allow the reaction to continue stirring at room temperature. After completion of the reaction, monitor thin-layer chromatography (TLC). Purify the resulting axially chiral allene product using flash silica gel column chromatography with ethyl acetate and petroleum ether as eluent. Calculate yield by weight, and determine ee (ee) using high-performance liquid chromatography (HPLC) with a chiral column.

[0056] In a typical embodiment of the present invention, a method for preparing an optimized trisubstituted axial chiral allenol derivative is provided, the method comprising the following steps: Figure 4 :

[0057] First, reaction conditions were optimized using phenyl-substituted allenyl dimethylene cyclic carbonate 1a and 2-pyridone 2a as template substrates. Using 0.10 mmol of phenyl-substituted allenyl dimethylene cyclic carbonate 1a and 0.25 mmol of 2-pyridone 2a, optimal reaction conditions were achieved by screening factors such as the type of palladium catalyst, chiral ligand, and reaction solvent. Ultimately, the trisubstituted axial chiral allenol product 4aa was obtained in 94% yield and 95% ee.

[0058] In order to enable those skilled in the art to more clearly understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below with reference to specific embodiments.

[0059] Example 1

[0060] Synthesis routes of novel allenyl dimethylene cyclic carbonate compounds with different substitutions, such as Figure 2 As shown:

[0061] In a 100 ml round-bottom flask filled with argon, tetrakis(triphenylphosphine)palladium (0.2 equivalents) and zinc bromide (2.0 equivalents) were added in sequence, then dissolved in ultra-dry tetrahydrofuran and cooled to 0 o C, slowly add the corresponding Grignard reagent solution (1.5 equivalents) dropwise and continue stirring to react for 20 minutes. o At 40°C, 5-ethynyl-2,2-dimethyl-1,3-dioxane-5-acetate (1.0 equivalent) obtained in the previous step was dissolved in ultra-dry tetrahydrofuran and added to the reaction solution. The mixture was stirred at room temperature overnight. After completion of the reaction, which was monitored by thin-layer chromatography (TLC), saturated ammonium chloride solution was added to quench the reaction. The organic phase was separated, and the aqueous phase was extracted with ethyl acetate. The combined organic phases were dried over anhydrous sodium sulfate and concentrated on a rotary evaporator under reduced pressure to remove the solvent. The crude product was redissolved in methanol and cooled to 0 o C., a drop of concentrated sulfuric acid was added dropwise, and the reaction mixture was stirred for approximately 30 minutes. After completion of the reaction, which was monitored by thin-layer chromatography (TLC), ethyl acetate was added to dilute the mixture, and the mixture was washed with saturated sodium bicarbonate solution. After separation and extraction, the combined organic phases were dried over anhydrous sodium sulfate, concentrated under reduced pressure to remove the solvent, and then subjected to silica gel column chromatography (ethyl acetate / petroleum ether = 50%) to separate and purify the allenedimethylene glycol product. Next, in a 100 ml round-bottom flask, the allenedimethylene glycol product obtained in the previous step was dissolved in dichloromethane and cooled to 0. o C, slowly add triethylamine (10.0 equivalents) dropwise. After stirring for 10 minutes, triphosgene (2.0 equivalents) is dissolved in dichloromethane and slowly added dropwise to the reaction system. After completion of the reaction, monitor by thin-layer chromatography (TLC). The reaction is quenched with saturated NHCl₄ solution, extracted with dichloromethane, and the combined organic phases are dried over sodium sulfate. After solvent removal by concentration under reduced pressure, the product is isolated and purified by silica gel column chromatography (ethyl acetate / petroleum ether = 15%) to obtain the allenyl dimethylene carbonate products with various substituents.

[0062] The synthesis results of novel allenyl dimethylene cyclic carbonate compounds containing different substitutions include the following compounds 1a~1n.

[0063] Compound 1a (5-(2-phenylvinylene)-1,3-dioxan-2-one) was prepared according to the general procedure described above and purified by column chromatography on silica gel (15% ethyl acetate / petroleum ether) to afford a white solid in 58% yield. MP = 57–59 °C; 1H NMR (800 MHz, CDCl3) δ 7.30 – 7.17 (m, 5H), 6.47 (d, J = 2.6 Hz, 1H), 4.95 – 4.87 (m, 4H). 13 C NMR (201 MHz, CDCl3) δ 199.3, 149.1, 131.7, 129.02, 129.00, 128.5, 127.4, 100.1, 100.0, 93.5, 68.32, 68.32. HRMS-ESI calculated: C 12 H 11 O3 + [M+H] + 203.0703, measured value: 203.0702.

[0064] 1b (5-(2-(3-fluorophenyl)vinylidene)-1,3-dioxan-2-one) was prepared according to the general procedure described above and purified by column chromatography on silica gel (15% ethyl acetate / petroleum ether) to give a viscous liquid in 58% yield. 1 H NMR (400 MHz, CDCl3) δ 7.39 – 7.28 (m, 1H), 7.09 – 7.04 (m,1H), 7.01 – 6.91 (m, 2H), 6.52 (t, J = 2.7 Hz, 1H), 5.05 – 4.95 (m, 4H). 13 CNMR (201 MHz, CDCl3) δ 199.2, 163.1 (d, J = 246.7 Hz), 149.0, 134.0 (d, J =7.8 Hz), 130.5 (d, J = 8.2 Hz), 123.2 (d, J = 2.9 Hz), 115.4 (d, J = 21.4Hz), 114.0 (d, J = 22.3 Hz), 99.4, 94.1, 68.1. 19 F NMR (376 MHz, CDCl3) δ -112.5. Electrospray ionization high-resolution mass spectrometry calculated: C 12 H9FNaO3 + [M+Na] +243.0428, measured value: 243.0431.

[0065] 1c (5-(2-(4-Fluorophenyl)vinylidene)-1,3-dioxan-2-one) was prepared according to the general procedure described above and purified by column chromatography on silica gel (15% ethyl acetate / petroleum ether) to give a viscous liquid in 48% yield. 1 H NMR (800 MHz, CDCl3) δ 7.35 – 7.19 (m, 2H), 7.05 (t, J = 8.6 Hz,2H), 6.52 (q, J = 2.7 Hz, 1H), 4.99 (d, J = 3.0 Hz, 4H). 13 C NMR (201 MHz, CDCl3) δ 198.9 (d, J = 2.3 Hz), 162.7 (d, J = 248.7 Hz), 149.0, 129.1 (d, J =8.3 Hz), 127.7 (d, J = 3.4 Hz), 116.1 (d, J = 22.1 Hz), 99.2, 93.8, 68.3. 19 FNMR (376 MHz, CDCl3) δ -112.6. Electrospray ionization high-resolution mass spectrometry calculated: C 12 H9FNaO3 + [M+Na] + 243.0428, measured value: 243.0438.

[0066] 1d (5-(2-(3-chlorophenyl)vinylidene)-1,3-dioxan-2-one) was prepared according to the general procedure described above and purified by column chromatography on silica gel (15% ethyl acetate / petroleum ether) to give a viscous liquid in 50% yield. 1 H NMR (400 MHz, CDCl3) δ 7.39 – 7.22 (m, 3H), 7.16 (dt, J =6.8, 1.8 Hz, 1H), 6.50 (p, J = 2.7 Hz, 1H), 5.07 – 4.94 (m, 4H). 13C NMR (201 MHz, CDCl3) δ 199.2, 149.1, 134.9, 133.6, 130.2, 128.5, 127.2, 125.6, 99.2,94.1, 68.1. Electrospray ionization high-resolution mass spectrometry calculated: C 12 H 10 ClO3 + [M+H] + 237.0313, measured value: 237.0304.

[0067] 1e (5-(2-(4-chlorophenyl)vinylidene)-1,3-dioxan-2-one) was prepared according to the general procedure described above and purified by column chromatography on silica gel (15% ethyl acetate / petroleum ether) to give a viscous liquid in 40% yield. 1 H NMR (800 MHz, CDCl3) δ 7.34 – 7.29 (m, 2H), 7.27 (s, 1H),7.21 (d, J = 8.5 Hz, 2H), 6.51 (p, J = 2.7 Hz, 1H), 5.02 – 4.96 (m, 4H). 13 CNMR (201 MHz, CDCl3) δ 199.2, 149.0, 134.2, 130.2, 129.2, 128.6, 99.3, 99.2,94.0, 68.1. Electrospray ionization high-resolution mass spectrometry calculated: C 12 H 10 ClO3 + [M+H] + 237.0313, measured value: 237.0311.

[0068] 1f (5-(2-(o-Tolyl)vinylidene)-1,3-dioxan-2-one) was prepared according to the general procedure described above and purified by column chromatography on silica gel (15% ethyl acetate / petroleum ether) to give a white solid in 60% yield. MP = 68–70 °C; 1 H NMR (800 MHz, CDCl3) δ 7.31 – 7.24 (m, 1H),7.19 (dd, J = 5.6, 3.4 Hz, 3H), 6.73 (p, J = 2.7 Hz, 1H), 4.98 (d, J= 2.9Hz, 4H), 2.37 (s, 3H). 13 C NMR (201 MHz, CDCl3) δ 120.0, 149.1, 135.8, 130.9, 130.1, 128.4, 128.0, 126.5, 97.6, 92.4, 68.5, 20.0. Electrospray ionization high-resolution mass spectrometry calculated: C 13 H 13 O3 + [M+H] + 217.0859, measured value: 217.0851.

[0069] 1 g of (5-(2-(m-tolyl)vinylidene)-1,3-dioxan-2-one) was prepared according to the general procedure above and purified by column chromatography on silica gel (15% ethyl acetate / petroleum ether) to give a viscous liquid in 50% yield. 1 H NMR (400 MHz, CDCl3) δ 7.25 – 7.21 (m, 1H), 7.15 – 7.03 (m,3H), 6.51 (p, J = 2.7 Hz, 1H), 4.99 (dd, J = 2.7, 1.3 Hz, 4H), 2.35 (s, 3H). 13 C NMR (201 MHz, CDCl3) δ 199.2, 149.1, 138.8, 131.5, 129.4, 128.9, 128.0,124.6, 100.2, 93.3, 68.4, 21.3. Electrospray ionization high-resolution mass spectrometry calculated: C 13 H 13 O3 + [M+H] + 217.0859, measured value: 217.0863.

[0070] 1h (5-(2-(p-Tolyl)vinylidene)-1,3-dioxan-2-one) was prepared according to the general procedure above and purified by column chromatography on silica gel (15% ethyl acetate / petroleum ether) to give a white solid. M.p. = 78 – 80 °C; 1 H NMR (800 MHz, CDCl3) δ 7.17 (t, J = 7.7 Hz, 4H), 6.52– 6.48 (m, 1H), 4.97 (q,J = 2.2 Hz, 4H), 2.35 (s, 3H). 13 C NMR (201 MHz,CDCl3) δ 199.1, 149.1, 138.6, 129.7, 128.6, 128.6, 127.3, 100.0, 99.92,99.91, 93.4, 77.3, 77.2, 77.0, 21.3. ESI-HRMS calculated: C 13 H 13 O3 + [M+H] + 217.0859, measured value: 217.0862.

[0071] 1i (5-(2-(2-methoxyphenyl)vinylidene)-1,3-dioxan-2-one) was prepared according to the general procedure described above and purified by column chromatography on silica gel (15% ethyl acetate / petroleum ether) to give a viscous liquid in 58% yield. 1 H NMR (800 MHz, CDCl3) δ 7.26 (s, 1H), 6.94 (d, J = 1.1 Hz, 2H), 6.89 (dd, J = 8.2, 1.1 Hz, 2H), 6.85 (t, J = 2.7 Hz, 1H), 4.97 (dd, J =5.8, 2.7 Hz, 4H), 3.85 (s, 3H). 13 C NMR (201 MHz, CDCl3) δ 200.5, 156.6, 149.2, 129.7, 128.7, 120.9, 120.1, 111.1, 94.4, 91.8, 68.7, 55.5. Electrospray ionization high-resolution mass spectrometry calculated: C 13 H 13 O4 + [M+H] + 233.0808, measured value: 233.0818.

[0072] 1j (5-(2-(3-methoxyphenyl)vinylidene)-1,3-dioxan-2-one) was prepared according to the general procedure described above and purified by column chromatography on silica gel (15% ethyl acetate / petroleum ether) to give a viscous liquid in 63% yield. 1 H NMR (800 MHz, CDCl3) δ 7.27 (t, J= 7.9 Hz, 1H), 6.93 –6.82 (m, 3H), 6.53 – 6.46 (m, 1H), 4.99 (dd, J = 6.9, 2.7 Hz, 4H), 3.81 (s,3H). 13 C NMR (201 MHz, CDCl3) δ 199.3, 160.0, 149.1, 133.0, 130.0, 12.0,113.9, 113.0, 100.1, 100.0, 93.5, 68.3, 55.3. ESI-HRMS calculated: C 13 H 13 O4 + [M+H] + 233.0808, measured value: 233.0807.

[0073] 1k (5-(2-(4-methoxyphenyl)vinylidene)-1,3-dioxan-2-one) was prepared according to the general procedure described above and purified by column chromatography on silica gel (15% ethyl acetate / petroleum ether) to give a viscous liquid in 52% yield. 1 H NMR (800 MHz, CDCl3) δ 7.24 – 7.15 (m, 2H), 6.93 – 6.84 (m,2H), 6.50 (q, J = 2.8 Hz, 1H), 5.00 – 4.84 (m, 4H), 3.81 (d, J = 1.9 Hz, 3H). 13 C NMR (201 MHz, CDCl3) δ 198.9, 159.9, 149.2, 128.7, 123.8, 114.5, 99.6,93.4, 68.5, 55.4. Electrospray ionization high-resolution mass spectrometry calculated: C 13 H 13 O4 + [M+H] + 233.0808, measured value: 233.0801.

[0074] 11-(5-(2-([1,1'-biphenyl]-4-yl)vinylene)-1,3-dioxan-2-one) was prepared according to the general procedure described above and purified by column chromatography on silica gel (15% ethyl acetate / petroleum ether) to give a white solid in 68% yield. M.p. = 118–120 °C;1 H NMR (400 MHz, CDCl3) δ 7.62 – 7.54(m, 4H), 7.49 – 7.41 (m, 2H), 7.39 – 7.31 (m, 3H), 6.59 (t, J = 2.7 Hz, 1H), 5.01 (dd, J = 2.6, 0.8 Hz, 4H). 13 C NMR (201 MHz, CDCl3) δ 199.4, 149.1, 141.4, 140.3, 130.6, 128.9, 127.9, 127.7, 127.0, 99.9, 93.6, 68.3. Electrospray ionization high-resolution mass spectrometry calculated: C 18 H 15 O3 + [M+H] + 279.1016, measured value: 279.1008.

[0075] 1m (5-(2-cyclohexylvinylidene)-1,3-dioxan-2-one) was prepared according to the general procedure above and purified by column chromatography on silica gel (15% ethyl acetate / petroleum ether) to give a viscous liquid in 60% yield. 1 H NMR (800 MHz, CDCl3) δ 5.54 (dp, J = 5.2, 2.5 Hz, 1H), 4.92 – 4.74 (m,4H), 2.16 – 2.02 (m, 1H), 1.79 – 1.56 (m, 5H), 1.45 – 1.23 (m, 2H), 1.20 –1.14 (m, 1H), 1.12 – 0.94 (m, 2H). 13 C NMR (201 MHz, CDCl3) δ 197.4, 149.2, 103.0, 90.2, 69.1, 37.0, 32.8, 25.9, 25.8. Electrospray ionization high-resolution mass spectrometry calculated: C 12 H 17 O3 + [M+H] + 209.1172, measured value: 209.1169.

[0076] 1n-(5-(2-(Naphthalen-2-yl)vinylidene)-1,3-dioxan-2-one) was prepared according to the general procedure described above and purified by column chromatography on silica gel (15% ethyl acetate / petroleum ether) to give a white solid in 64% yield. MP = 128–130 °C; 1 H NMR (600 MHz, CDCl3) δ 7.84 – 7.77 (m,3H), 7.69 (d, J = 1.8 Hz, 1H), 7.49 (t, J = 3.1 Hz, 2H), 7.39 (dd, J = 8.5,1.8 Hz, 1H), 6.75 – 6.63 (m, 1H), 5.02 (dd, J = 6.0, 2.7 Hz, 4H). 13 C NMR (201 MHz, CDCl3) δ 199.7, 149.1, 133.5, 133.2, 129.1, 128.8, 127.92, 127.86,127.0, 126.7, 126.6, 124.4, 100.5, 93.8, 68.4. ESI-HRMS calculated: C 16 H 13 O3 + [M+H] + 253.0859, measured value: 253.0857.

[0077] Example 2

[0078] like Figure 5 Under argon, allenyl dimethylene cyclic carbonate compound 1 (0.10 mmol), 2-pyridone or other nitrogen-containing heterocyclic substrate 2 or 3 (0.25 mmol), palladium catalyst tris(dibenzylideneacetone)dipalladium (5 mol%, 0.005 mmol) and ligand L1: (1R,2R)-(+)-1,2-diaminocyclohexane-N,N'-bis(2-phenylphosphino-1-naphthoyl) (11 mol%, 0.011 mmol) were weighed into a Shrek tube. 1 mL of dichloromethane was added, and the reaction was stirred continuously at room temperature. After completion of the reaction was monitored by thin-layer chromatography, the resulting axially chiral allene product 4 or 5 was purified by flash chromatography on silica gel using a 1:1 ethyl acetate / petroleum ether eluent. The yield was calculated by weight, and the ee value was determined using high-performance liquid chromatography with a chiral column.

[0079] The reaction results of the allenyl dimethylene cyclic carbonate compound and 2-pyridone include the following compounds 4aa~4na, 4ab~4az and 4aaa, 4aab, and 4aac.

[0080] 4aa ((R)-1-(2-(Hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)pyridin-2(1H)-one) was prepared according to the general procedure described above in 98% yield (24.8 mg) with 96% ee. Purification by flash silica gel column chromatography (50% ethyl acetate / petroleum ether) afforded a white solid. MP = 102–104°C; [α] 25 D = 33.2 ( c 0.64, dichloromethane); 1 H NMR (400 MHz, CDCl3) δ 7.39 (ddd, J = 8.9, 6.6, 2.0 Hz,1H), 7.35 – 7.16 (m, 6H), 6.64 (dt, J = 9.1, 1.0 Hz, 1H), 6.31 (t, J = 2.0Hz, 1H), 6.26 (td, J = 6.7, 1.4 Hz, 1H), 4.85 – 4.65 (m, 2H), 4.49 (d, J =4.3 Hz, 1H), 4.19 (d, J = 2.1 Hz, 2H). 13 C NMR (201 MHz, CDCl3) δ 202.9, 163.3, 140.4, 137.5, 133.3, 128.8, 127.6, 127.0, 120.8, 107.63, 105.0, 96.9, 61.0, 48.9. ESI-HRMS calculated: C 16 H 16 NO2 + [M+H] + 254.1176, found: 254.1166. HPLC analysis: 96% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 9.333 min (minor peak), 9.87 min (major peak).

[0081] 4ba ((R)-1-(4-(3-fluorophenyl)-2-(hydroxymethyl)buta-2,3-dien-1-yl)pyridin-2(1H)-one) was prepared according to the general procedure described above in 90% yield (24.4 mg) with 95% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid; [α] 25 D = 53.3 ( c 0.77, dichloromethane); 1 H NMR (600 MHz, CDCl3) δ 7.43 – 7.21 (m, 3H), 7.04 – 6.86 (m, 3H), 6.64(dd, J = 9.2, 1.4 Hz, 1H), 6.28 – 6.20 (m, 2H), 4.83 – 4.67 (m, 2H), 4.58 (s,1H), 4.20 (t, J = 1.9 Hz, 2H). 13 C NMR (201 MHz, CDCl3) δ 203.1, 163.3, 162.9(d, J = 154.8 Hz), 140.4, 137.4, 135.8 (d, J = 7.9 Hz), 130.2 (d, J = 8.2Hz), 122.7 (d, J = 3.2 Hz), 120.9, 114.5 (d, J = 21.5 Hz), 113.5 (d, J = 22.3Hz), 107.6, 105.6, 96.2 (d, J = 2.9 Hz), 60.9, 48.8. 19 F NMR (376 MHz, CDCl3)δ -113.1. Electrospray ionization high-resolution mass spectrometry calculated value: C 16 H 15 FNO2 + [M+H] + 272.1081, found: 272.1072. HPLC analysis: 95% ee (IA, 15% isopropanol / n-hexane, 1.0 ml / min, UV: 254 nm), t R = 10.403 min (minor peak), 10.657 min (major peak).

[0082] 4ca ((R)-1-(4-(4-Fluorophenyl)-2-(hydroxymethyl)buta-2,3-dien-1-yl)pyridin-2(1H)-one) was prepared using the general procedure described above in 96% yield (26.1 mg) with 94% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 48.0 ( c 0.75, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.39 (ddd, J = 8.9, 6.6, 2.0 Hz, 1H), 7.32 (dd, J =6.8, 2.0 Hz, 1H), 7.19 (dd, J = 8.6, 5.4 Hz, 2H), 6.98 (t, J = 8.6 Hz, 2H),6.63 (dd, J = 9.3, 1.4 Hz, 1H), 6.27 (t, J = 2.1 Hz, 1H), 6.26 (td, J = 6.7,1.4 Hz, 1H), 4.78 – 4.68 (m, 2H), 4.55 (s, 1H), 4.23 – 4.13 (m, 2H). 13 C NMR (201 MHz, CDCl3) δ 202.6 (d, J = 2.3 Hz), 163.3, 162.2 (d, J = 246.8 Hz),140.4, 137.5, 129.2 (d, J = 3.1 Hz), 128.5 (d, J = 8.1 Hz), 120.8, 115.8 (d, J = 21.8 Hz), 107.5, 105.4, 96.1, 61.1, 48.9. 19 F NMR (376 MHz, CDCl3) δ -114.2. Electrospray ionization high-resolution mass spectrometry calculated: C 16 H 15 FNO2 + [M+H] +272.1081, found: 272.1087. HPLC analysis: 94% ee (AS-H, 15% isopropanol / n-hexane, 1.0 ml / min, UV: 254 nm), t R = 19.403 min (minor peak), 14.660 min (major peak).

[0083] 4da ((R)-1-(4-(3-chlorophenyl)-2-(hydroxymethyl)buta-2,3-dien-1-yl)pyridin-2(1H)-one) was prepared according to the general procedure described above in 98% yield (28.1 mg) with 96% ee. Purification by flash silica gel column chromatography (50% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 58.8 ( c 0.91, dichloromethane); 1 H NMR (600 MHz, CDCl3) δ 7.42 – 7.30 (m, 2H), 7.23 – 7.17 (m, 3H), 7.11(dt, J = 7.5, 1.5 Hz, 1H), 6.64 (dd, J = 9.2, 1.3 Hz, 1H), 6.27 (td, J = 6.7,1.4 Hz, 1H), 6.25 (t, J = 2.1 Hz, 1H), 4.81 – 4.66 (m, 2H), 4.60 (s, 1H), 4.20 (t, J = 2.4 Hz, 2H). 13 C NMR (201 MHz, CDCl3) δ 203.1, 163.3, 140.4,137.4, 135.4, 134.7, 130.0, 127.6, 126.8, 125.1, 120.9, 107.6, 105.7, 96.1,60.9, 48.8. ESI-HRMS calculated: C 16 H 14 ClNNaO2 + [M+Na] + 310.0605, found: 310.0605. HPLC analysis: 96% ee (IA, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R= 10.693 min (minor peak), 11.127 min (major peak).

[0084] Following the general procedure described above, 4ea ((R)-1-(4-(4-chlorophenyl)-2-(hydroxymethyl)buta-2,3-dien-1-yl)pyridin-2(1H)-one) was prepared in 86% yield (24.7 mg) with 99% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 30.9 ( c 1.39, dichloromethane); 1 H NMR (600 MHz, CDCl3) δ 7.43 – 7.09 (m, 6H), 6.63 (d, J = 9.1 Hz, 1H), 6.29 – 6.21 (m, 2H), 4.87 – 4.62 (m, 2H), 4.55 (d, J = 7.9 Hz, 1H), 4.20 (s,2H). 13 C NMR (201 MHz, CDCl3) δ 202.9, 163.2, 140.4, 137.4, 133.2, 131.9,128.95, 128.93, 128.1, 120.9, 107.6, 105.6, 96.2, 61.0, 48.8. ESI-HRMS calculated: C 16 H 14 ClNNaO2 + [M+Na] + 310.0605, found: 310.0596. HPLC analysis: 99% ee (AS-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 14.313 min (main peak).

[0085] 4fa ((R)-1-(2-(hydroxymethyl)-4-(o-tolyl)buta-2,3-dien-1-yl)pyridin-2(1H)-one) was prepared according to the general procedure described above in 99% yield (26.4 mg) with 97% ee. Purification by flash silica gel column chromatography (50% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 57.1 ( c 0.87, dichloromethane);1 HNMR (800 MHz, CDCl3) δ 7.41 – 7.31 (m, 2H), 7.27 – 7.25 (m, 1H), 7.13 (pd, J = 5.1, 2.5 Hz, 3H), 6.66 – 6.61 (m, 1H), 6.50 (p, J = 2.0 Hz, 1H), 6.26 (td, J = 6.7, 1.4 Hz, 1H), 4.81 – 4.68 (m, 2H), 4.57 (t, J = 6.8 Hz, 1H), 4.22 –4.14 (m, 2H), 2.33 (s, 3H). 13 C NMR (201 MHz, CDCl3) δ 203.6, 163.3, 140.3,137.5, 135.3, 131.5, 130.7, 127.5, 127.4, 126.3, 120.8, 107.5, 103.9, 94.2,61.2, 49.0, 19.9. ESI-HRMS calculated: C 17 H 18 NO2 + [M+H] + 268.1332, found: 268.1334. HPLC analysis: 97% ee (AS-H, 15% isopropanol / n-hexane, 1.0 ml / min, UV: 254 nm), t R = 18.547 min (minor peak), 17.377 min (major peak).

[0086] 4ga ((R)-1-(2-(hydroxymethyl)-4-(m-tolyl)buta-2,3-dien-1-yl)pyridin-2(1H)-one) was prepared according to the general procedure described above in 99% yield (26.4 mg) with 95% ee. Purification by flash silica gel column chromatography (50% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 51.0 ( c 0.74, dichloromethane); 1 H NMR (600 MHz, CDCl3) δ 7.60 – 7.29 (m, 2H), 7.23 – 6.95 (m, 4H), 6.64 (d, J= 9.3 Hz, 1H), 6.38 – 6.22 (m, 2H), 4.87 – 4.68 (m, 2H), 4.60 (s,1H), 4.31 – 4.12 (m, 2H), 2.31 (s, 3H). 13 C NMR (201 MHz, CDCl3) δ 202.9, 163.3, 140.4, 138.4, 137.5, 133.2, 128.7, 128.4, 127.6, 124.1, 120.8, 107.5, 104.9, 96.9, 61.1, 49.0, 21.33, 21.32. ESI-HRMS calculated: C 17 H 18 NO2 + [M+H] + 268.1332, found: 268.1323. HPLC analysis: 95% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 7.870 min (minor peak), 8.347 min (major peak).

[0087] 4ha (( R )-1-(2-(hydroxymethyl)-4-(p-tolyl)buta-2,3-dien-1-yl)pyridin-2(1H)-one was obtained in 92% yield (24.6 mg) with an ee of 97%. Purification by flash silica gel column chromatography (50% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 51.7 ( c 0.73, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.39 (ddd, J = 8.9,6.6, 2.1 Hz, 1H), 7.33 (dd, J = 6.7, 2.1 Hz, 1H), 7.14 – 7.09 (m, 4H), 6.65 –6.62 (m, 1H), 6.28 (t, J = 2.0 Hz, 1H), 6.26 – 6.23 (m, 1H), 4.74 (ddd, J=69.0, 14.1, 2.0 Hz, 2H), 4.57 (s, 1H), 4.18 (t, J = 2.1 Hz, 2H), 2.33 (s,3H). 13 C NMR (201 MHz, CDCl3) δ 202.7, 163.3, 140.3, 137.5, 137.5, 130.3,129.5, 126.9, 120.8, 107.5, 104.9, 96.8, 61.1, 49.0, 21.2. ESI-HRMS calculated: C 17 H 18 NO2 + [M+H] + 268.1332, found: 268.1336. HPLC analysis: 97% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 8.630 min (minor peak), 8.953 min (major peak).

[0088] 4ja ((R)-1-(2-(hydroxymethyl)-4-(3-methoxyphenyl)buta-2,3-dien-1-yl)pyridin-2(1H)-one) was prepared using the general procedure described above in 85% yield (24.1 mg) and 96% ee. Purification by flash silica gel column chromatography (50% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 30.0 ( c 1.00, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.39 (ddd, J = 8.9, 6.6, 2.1 Hz, 1H), 7.33 (dd, J = 6.8, 2.1 Hz, 1H), 7.22 – 7.18 (m, 1H), 6.83 (dt, J = 7.7, 1.3 Hz, 1H),6.77 (tdd, J = 3.9, 2.6, 0.9 Hz, 2H), 6.63 (dt, J = 9.1, 1.0 Hz, 1H), 6.28(p, J = 2.1 Hz, 1H), 6.26 (td, J= 6.7, 1.4 Hz, 1H), 4.74 (ddd, J = 118.5,14.2, 2.0 Hz, 2H), 4.55 (s, 1H), 4.19 (s, 2H), 3.78 (s, 3H). 13 C NMR (201 MHz,CDCl3) δ 203.0, 163.3, 160.0, 140.4, 137.5, 134.8, 129.7, 120.8, 119.6,113.4, 112.11, 107.6, 105.1, 97.0, 61.1, 55.3, 48.9. ESI-HRMS calculated: C 17 H 18 NO3 + [M+H] + 284.1281, found: 284.1271. HPLC analysis: 96% ee (AS-H, 15% isopropanol / n-hexane, 1.0 ml / min, UV: 254 nm), t R = 25.790 min (minor peak), 21.730 min (major peak).

[0089] 4ka ((R)-1-(2-(hydroxymethyl)-4-(4-methoxyphenyl)buta-2,3-dien-1-yl)pyridin-2(1H)-one) was prepared using the general procedure described above in 92% yield (26.1 mg) with 95% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 51.8 ( c 1.11, dichloromethane); 1 H NMR (600 MHz, CDCl3) δ 7.38 (ddd, J = 8.9, 6.8, 2.0 Hz, 1H), 7.36 –7.30 (m, 1H), 7.16 (d, J = 8.2 Hz, 2H), 6.83 (d, J = 8.8 Hz, 2H), 6.63 (d, J = 9.1 Hz, 1H), 6.27 (d, J = 3.1 Hz, 1H), 6.25 (d, J= 7.0 Hz, 1H), 4.82 –4.66 (m, 2H), 4.54 (s, 1H), 4.18 (s, 2H), 3.80 (d, J = 2.0 Hz, 3H). 13 C NMR (201 MHz, CDCl3) δ 202.3, 163.3, 159.2, 140.3, 137.5, 128.1, 125.5, 120.8,114.3, 107.5, 105.00, 105.00, 96.5, 61.2, 55.4, 49.0. Electrospray ionization high-resolution mass spectrometry calculated: C 17 H 18 NO3 + [M+H] + 284.1281, found: 284.1288. HPLC analysis: 95% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 12.583 min (minor peak), 13.333 min (major peak).

[0090] Following the general procedure described above, 4la ((R)-1-(4-([1,1'-biphenyl]-4-yl)-2-(hydroxymethyl)buta-2,3-dien-1-yl)pyridin-2(1H)-one) was prepared in 96% yield (31.6 mg) with 95% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 38.7 ( c 0.91, dichloromethane); 1 H NMR (600 MHz, CDCl3) δ 7.55 (dd, J = 25.4, 7.8 Hz, 4H), 7.50 –7.23 (m, 7H), 6.64 (d, J = 9.1 Hz, 1H), 6.35 (s, 1H), 6.26 (t, J = 6.8 Hz,1H), 4.84 – 4.70 (m, 2H), 4.59 (s, 1H), 4.21 (s, 2H). 13C NMR (201 MHz, CDCl3)δ 203.1, 163.3, 140.5, 140.4, 140.4, 137.5, 132.3, 128.6, 127.5, 127.5,127.4, 126.9, 120.9, 107.6, 105.2, 96.6, 61.1, 49.0. ESI-HRMS calculated: C 22 H 20 NO2 + [M+H] + 330.1489, found: 330.1475. HPLC analysis: 95% ee (AS-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 26.167 min (minor peak), 21.130 min (major peak).

[0091] 4ma ((R)-1-(4-cyclohexyl-2-(hydroxymethyl)but-2,3-dien-1-yl)pyridin-2(1H)-one) was prepared according to the general procedure described above in 92% yield (23.8 mg) with 93% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = -7.1 ( c 1.07, dichloromethane); 1 HNMR (800 MHz, CDCl3) δ 7.39 (ddd, J = 8.9, 6.6, 2.1 Hz, 1H), 7.31 (dd, J =6.8, 2.1 Hz, 1H), 6.62 (dd, J = 9.1, 1.4 Hz, 1H), 6.27 (td, J = 6.7, 1.4 Hz,1H), 5.30 (dp, J = 6.2, 2.1 Hz, 1H), 4.71 – 4.54 (m, 2H), 4.26 (t, J = 6.8Hz, 1H), 4.05 (dd, J = 6.7, 2.1 Hz, 2H), 1.97 (dddt, J= 11.3, 9.2, 6.3, 3.2Hz, 1H), 1.72 – 1.56 (m, 5H), 1.29 – 1.19 (m, 3H), 1.13 (dddd, J = 15.9,12.5, 7.9, 3.4 Hz, 1H), 1.00 (dddd, J = 19.4, 13.9, 8.1, 3.7 Hz, 2H). 13 C NMR (201 MHz, CDCl3) δ 200.6, 163.2, 140.1, 137.7, 120.8, 107.2, 101.9, 100.1,61.8, 61.7, 49.3, 37.2, 33.0, 32.9, 26.0, 25.9. Electrospray ionization high-resolution mass spectrometry calculated: C 16 H 22 NO2 + [M+H] + 260.1645, found: 260.1640. HPLC analysis: 93% ee (AS-H, 15% isopropanol / n-hexane, 1.0 ml / min, UV: 254 nm), t R = 13.503 min (minor peak), 10.600 min (major peak).

[0092] 4na ((R)-1-(2-(hydroxymethyl)-4-(naphthalen-2-yl)buta-2,3-dien-1-yl)pyridin-2(1H)-one) was prepared according to the general procedure described above in 96% yield (29.1 mg) with 90% ee. Purification by flash silica gel column chromatography (50% ethyl acetate / petroleum ether) afforded a white solid. MP = 124–126°C; [α] 25 D = 59.3( c 2.00, CHCl3); 1 H NMR (600 MHz, DMSO- d 6) δ 7.92 – 7.58 (m, 5H), 7.49 – 7.38 (m, 3H), 7.27 (ddd, J = 8.9, 6.5, 2.1 Hz, 1H), 6.48 (p, J = 2.8 Hz, 1H), 6.32(dd, J = 9.2, 1.4 Hz, 1H), 6.09 (td,J = 6.7, 1.4 Hz, 1H), 5.29 (t, J = 5.9Hz, 1H), 4.70 (dd, J = 5.5, 3.2 Hz, 2H), 4.16 (dd, J = 5.9, 2.4 Hz, 2H). 13 CNMR (201 MHz, DMSO) δ 201.9, 161.7, 140.4, 139.7, 133.6, 132.7, 132.1, 128.4,128.1, 128.0, 126.8, 126.3, 125.9, 125.2, 120.0, 108.2, 105.5, 98.7, 61.1,47.5. ESI-HRMS calculated: C 20 H 18 NO2 + [M+H] + 304.1332, found: 304.1339. HPLC analysis: 90% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 12.757 min (minor peak), 13.797 min (major peak).

[0093] 4ab ((R)-3-Fluoro-1-(2-(hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)pyridin-2(1H)-one) was prepared according to the general procedure described above in 95% yield (25.7 mg) with 93% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a white solid. Melting point = 108–110°C; [α] 25 D = 94.6 ( c 0.81, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.33 – 7.28 (m, 2H), 7.26 – 7.07(m, 5H), 6.36 – 6.27 (m, 1H), 6.16 (td, J = 7.2, 4.4 Hz, 1H), 4.80 (ddd, J =52.3, 14.3, 2.1 Hz, 2H), 4.23 (s, 2H), 4.00 (d, J= 7.3 Hz, 1H). 13 C NMR (201MHz, CDCl3) δ 202.9, 156.8 (d, J = 25.3 Hz), 152.2 (d, J = 250.5 Hz), 133.1,132.8 (d, J = 5.0 Hz), 128.8, 127.7, 127.0, 121.0 (d, J = 17.0 Hz), 105.1 (d, J = 5.8 Hz), 104.9, 97.6, 61.2, 48.8. 19 F NMR (376 MHz, CDCl3) δ -129.8. Electrospray ionization high-resolution mass spectrometry calculated: C 16 H 15 FNO2 + [M+H] + 272.1081, found: 272.1073. HPLC analysis: 93% ee (AD-H, 10% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 12.643 min (minor peak), 13.463 min (major peak).

[0094] Following the general procedure described above, 4ac ((R)-4-fluoro-1-(2-(hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)pyridin-2(1H)-one) was prepared in 96% yield (26.4 mg) with 96% ee. Purification by flash silica gel column chromatography (50% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 72.4 ( c 0.80, dichloromethane); 1 HNMR (800 MHz, CDCl3) δ 7.36 (t, J = 7.5 Hz, 1H), 7.32 – 7.28 (m, 2H), 7.23(ddt, J = 7.2, 3.2, 1.5 Hz, 3H), 6.32 (p, J = 2.1 Hz, 1H), 6.26 (dd, J =10.6, 2.8 Hz, 1H), 6.14 (ddd, J= 7.6, 6.0, 2.8 Hz, 1H), 4.73 (ddd, J = 58.1,14.4, 2.1 Hz, 2H), 4.21 (dd, J = 5.8, 2.0 Hz, 2H), 4.08 (t, J = 6.9 Hz, 1H). 13 C NMR (201 MHz, CDCl3) δ 202.9, 170.5 (d, J = 268.8 Hz), 164.4 (d, J = 19.1Hz), 139.3 (d, J = 13.4 Hz), 133.1, 128.8, 127.7, 127.0, 105.0, 103.5 (d, J =17.0 Hz), 99.9 (d, J = 27.3 Hz), 97.5, 61.2, 48.4. 19 F NMR (376 MHz, CDCl3) δ-95.2. Electrospray ionization high-resolution mass spectrometry calculated: C 16 H 15 FNO2 + [M+H] + 272.1081, found: 272.1089. HPLC analysis: 96% ee (AS-H, 15% isopropanol / n-hexane, 1.0 ml / min, UV: 254 nm), t R = 13.310 min (minor peak), 16.770 min (major peak).

[0095] 4ad ((R)-5-fluoro-1-(2-(hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)pyridin-2(1H)-one) was prepared using the general procedure described above in 98% yield (26.6 mg) with 99% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 38.0 ( c 0.60, dichloromethane); 1HNMR (800 MHz, CDCl3) δ 7.39 – 7.29 (m, 3H), 7.25 (q, J = 7.7, 6.8 Hz, 4H), 6.62 (dd, J = 10.0, 5.2 Hz, 1H), 6.34 (t, J = 2.2 Hz, 1H), 4.71 (qd, J =14.2, 2.0 Hz, 2H), 4.29 – 4.10 (m, 3H). 13 C NMR (201 MHz, CDCl3) δ 203.0,161.3, 148.0 (d, J = 234.2 Hz), 133.0, 132.1 (d, J = 23.7 Hz), 128.9, 127.8,127.0, 122.7 (d, J = 36.9 Hz), 121.5 (d, J = 7.3 Hz), 104.6, 97.2, 61.0,49.3. 19 F NMR (376 MHz, CDCl3) δ -146.4. Electrospray ionization high-resolution mass spectrometry calculated: C 16 H 15 FNO2 + [M+H] + 272.1081, found: 272.1091. HPLC analysis: 99% ee (OD-H, 10% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 20.313 min (main peak).

[0096] Following the general procedure described above, 4ae ((R)-3-chloro-1-(2-(hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)pyridin-2(1H)-one) was prepared in 95% yield (27.2 mg) with 96% ee. Purification by flash silica gel column chromatography (40% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 40.5 ( c 0.89, dichloromethane); 1 HNMR (600 MHz, CDCl3) δ 7.55 (dd, J = 7.5, 2.0 Hz, 1H), 7.41 – 7.12 (m, 6H), 6.32 (d, J= 3.2 Hz, 1H), 6.20 (t, J = 7.1 Hz, 1H), 4.94 – 4.69 (m, 2H), 4.23 (s, 2H), 3.84 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 203.0, 159.6, 138.4, 136.2, 133.0, 128.8, 127.7, 127.0, 126.4, 106.5, 105.0, 97.7, 61.3, 49.8. ESI-HRMS calculated: C 16 H 14 ClNNaO2 + [M+Na] + 310.0605, 310.0608. HPLC 96% ee (AS-H, 10% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 20.233 min (minor peak), 16.583 min (major peak).

[0097] 4af ((R)-4-chloro-1-(2-(hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)pyridin-2(1H)-one) was prepared using the general procedure described above in 95% yield (27.3 mg) with 93% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 68.7 ( c 0.68, dichloromethane); 1 H NMR (600 MHz, CDCl3) δ 7.35 – 7.21 (m, 6H), 6.66 (d, J = 2.4 Hz, 1H),6.32 (t, J = 2.2 Hz, 1H), 6.26 (dd, J = 7.3, 2.3 Hz, 1H), 4.82 – 4.62 (m,2H), 4.20 (s, 2H), 4.06 (s, 1H). 13C NMR (201 MHz, CDCl3) δ 202.9, 162.2,147.5, 137.6, 133.1, 128.8, 127.7, 127.0, 119.4, 109.2, 104.9, 97.4, 61.1,48.6. Electrospray ionization high-resolution mass spectrometry calculated: C 16 H 14 ClNNaO2 + [M+Na] + 310.0605, found: 310.0595. HPLC analysis: 93% ee (AS-H, 5% isopropanol / n-hexane, 1.0 ml / min, UV: 254 nm), t R = 30.070 min (minor peak), 27.190 min (major peak).

[0098] Following the general procedure described above, 4ag ((R)-5-chloro-1-(2-(hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)pyridin-2(1H)-one) was prepared in 98% yield (28.1 mg) with 96% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 71.6 ( c 1.15, CHCl3); 1 H NMR (800 MHz, CDCl3) δ 7.37 (d, J = 2.8 Hz, 1H), 7.34 – 7.18 (m, 6H), 6.59 (d, J = 9.6 Hz, 1H), 6.34 (p, J = 2.1 Hz, 1H), 4.75 – 4.67 (m, 2H), 4.20 (t, J =2.3 Hz, 2H), 3.41 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 202.9, 161.6, 141.2,134.9, 133.0, 128.9, 127.8, 127.0, 121.6, 113.8, 104.8, 97.5, 61.1, 49.0. Electrospray ionization high-resolution mass spectrometry calculated: C 16 H 15 ClNO2 + [M+H] +288.0786, found: 288.0776. HPLC analysis: 96% ee (IA, isopropanol / n-hexane, 1.0 ml / min, UV: 254 nm), t R = 8.437 min (minor peak), 8.640 min (major peak).

[0099] 4ah ((R)-6-chloro-1-(2-(hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)pyridin-2(1H)-one) was prepared using the general procedure described above in 95% yield (27.2 mg) with 82% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 76.5 ( c 0.71, dichloromethane); 1 HNMR (600 MHz, CDCl3) δ 7.51 – 7.16 (m, 6H), 6.54 (dd, J = 9.1, 2.8 Hz, 1H), 6.46 – 6.25 (m, 2H), 5.19 – 4.97 (m, 2H), 4.20 (s, 2H), 3.91 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 203.2, 163.8, 139.5, 138.2, 133.2, 128.6, 127.5, 127.2,118.4, 108.0, 104.0, 97.5, 61.4, 45.4. Electrospray ionization high-resolution mass spectrometry calculated: C 16 H 15 ClNNaO2 + [M+Na] + 310.0605, found: 310.0600. HPLC analysis: 82% ee (AS-H, 10% isopropanol / n-hexane, 1.0 ml / min, UV: 254 nm), t R = 22.930 min (minor peak), 20.800 min (major peak).

[0100] Following the general procedure described above, 4ai ((R)-3-bromo-1-(2-(hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)pyridin-2(1H)-one) was prepared in 98% yield (32.4 mg) with 95% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 27.5 ( c 1.10, dichloromethane); 1 H NMR (600 MHz, CDCl3) δ 7.75 (d, J = 7.2 Hz, 1H), 7.57 – 7.15 (m, 6H), 6.31(s, 1H), 6.13 (t, J = 7.1 Hz, 1H), 4.96 – 4.69 (m, 2H), 4.23 (s, 2H), 3.96(s, 1H). 13 C NMR (201 MHz, CDCl3) δ 203.0, 159.6, 142.3, 137.1, 133.0, 128.8, 127.7, 127.0, 116.4, 107.2, 105.0, 97.7, 61.3, 50.1. ESI-HRMS calculated: C 16 H 15 BrNO2 + [M+H] + 332.0281, found: 332.0290. HPLC analysis: 95% ee (IA, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 9.310 min (minor peak), 9.637 min (major peak).

[0101] Following the general procedure described above, 4aj ((R)-4-bromo-1-(2-(hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)pyridin-2(1H)-one) was prepared in 98% yield (32.4 mg) with 94% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 64.3 ( c 0.81, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.36 – 7.17 (m, 6H), 6.87 (d,J = 2.2 Hz, 1H), 6.39(dd, J = 7.3, 2.1 Hz, 1H), 6.32 (t, J = 2.1 Hz, 1H), 4.70 (ddd, J = 61.8,14.3, 2.1 Hz, 2H), 4.20 (s, 2H), 4.08 (s, 1H) 13 C NMR (201 MHz, CDCl3) δ202.9, 161.9, 137.3, 136.3, 133.1, 128.8, 127.7, 126.98, 126.96, 122.9,111.7, 104.8, 97.5, 61.1, 48.0. Electrospray ionization high-resolution mass spectrometry calculated: C 16 H 15 BrNO2 + [M+H] + 332.0281, found: 332.0288. HPLC analysis: 94% ee (IB, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 9.980 min (minor peak), 10.980 min (major peak).

[0102] 4ak ((R)-5-bromo-1-(2-(hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)pyridin-2(1H)-one) was prepared using the general procedure described above in 98% yield (32.4 mg) with 96% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 114.1 ( c 1.21, dichloromethane); 1 H NMR (600 MHz, CDCl3) δ 7.45 (d, J = 2.7 Hz, 1H), 7.38 (dd, J = 9.6, 2.7 Hz,1H), 7.34 – 7.15 (m, 5H), 6.53 (d, J = 9.6 Hz, 1H), 6.34 (s, 1H), 4.71 (q, J = 14.2 Hz, 2H), 4.20 (s, 2H), 4.08 (s, 1H).13 C NMR (201 MHz, CDCl3) δ 202.9,161.7, 143.3, 137.3, 133.0, 128.9, 127.8, 127.0, 122.0, 104.9, 99.3, 97.6,61.1, 48.9. Electrospray ionization high-resolution mass spectrometry calculated value: C 16 H 15 BrNO2 + [M+H] + 332.0281, found: 332.0280. HPLC analysis: 96% ee (IA, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 8.710 min (minor peak), 8.903 min (major peak).

[0103] 4al ((R)-6-bromo-1-(2-(hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)pyridin-2(1H)-one) was prepared using the general procedure described above in 95% yield (31.4 mg) with 92% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 102.7 ( c 0.85, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.39 – 7.11 (m, 6H), 6.66 – 6.44 (m, 2H), 6.30 (p, J = 2.2 Hz, 1H), 5.24 – 5.00 (m, 2H), 4.20 (d, J = 2.1 Hz, 2H), 4.03 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 203.3, 163.7, 139.9, 133.1, 128.6, 127.6, 127.5,127.3, 118.8, 112.4, 104.1, 97.7, 61.5, 48.3. ESI-HRMS calculated: C 16 H 15 BrNO2 + [M+H] +332.0281, found: 332.0278. HPLC analysis: 92% ee (OD-H, 15% isopropanol / n-hexane, 1.0 ml / min, UV: 254 nm), t R = 11.393 min (minor peak), 10.283 min (major peak).

[0104] 4am ((R)-1-(2-(Hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)-3-methylpyridin-2(1H)-one) was prepared according to the general procedure described above in 87% yield (23.2 mg) with 96% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 19.4 ( c 0.80, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.30 – 7.20 (m, 7H), 6.29 (t, J = 2.0 Hz, 1H),6.19 (t, J = 6.7 Hz, 1H), 4.76 (ddd, J = 89.9, 14.1, 1.9 Hz, 3H), 4.18 (dd, J = 3.2, 2.1 Hz, 2H), 2.18 (s, 3H). 13 C NMR (201 MHz, CDCl3) δ 202.9, 163.6, 137.7, 134.8, 133.4, 129.9, 128.8, 127.5, 127.0, 107.3, 105.1, 96.7, 61.1, 49.2, 17.3. Electrospray ionization high-resolution mass spectrometry calculated: C 17 H 18 NO2 + [M+H] + 268.1332, found: 268.1328. HPLC analysis: 96% ee (IB, 15% isopropanol / n-hexane, 1.0 ml / min, UV: 254 nm), t R = 8.030 min (minor peak), 8.357 min (major peak).

[0105] 4an ((R)-1-(2-(Hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)-4-methylpyridin-2(1H)-one) was prepared using the general procedure described above in 73% yield (19.5 mg) with 96% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 25.8 ( c 1.51, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.30 (t, J = 7.5 Hz, 2H), 7.26 – 7.14 (m,4H), 6.45 (s, 1H), 6.29 (t, J = 2.1 Hz, 1H), 6.12 (dd, J = 7.0, 1.9 Hz, 1H),4.71 (ddd, J = 79.4, 14.2, 1.9 Hz, 3H), 4.17 (t, J = 2.2 Hz, 2H), 2.20 (d, J = 1.3 Hz, 3H). 13 C NMR (201 MHz, CDCl3) δ 202.8, 163.3, 152.3, 136.3, 133.4,128.8, 127.5, 126.96, 126.94, 119.1, 110.2, 105.1, 96.7, 96.6, 60.9, 48.5,21.3. ESI-HRMS calculated: C 17 H 18 NO2 + [M+H] + 268.1332, found: 268.1336. HPLC analysis: 96% ee (IB, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 11.073 min (minor peak), 11.534 min (major peak).

[0106] Following the general procedure described above, 4ao ((R)-1-(2-(Hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)-5-methylpyridin-2(1H)-one) was prepared in 92% yield (24.6 mg) with 94% ee. Purification by flash silica gel column chromatography (50% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 42.0 ( c 0.72, dichloromethane); 1 H NMR (600 MHz, CDCl3) δ 7.34 – 7.17 (m, 6H), 7.09 (dd, J = 2.5, 1.3 Hz,1H), 6.59 (d, J = 9.2 Hz, 1H), 6.31 (q, J = 2.0 Hz, 1H), 4.79 – 4.62 (m, 3H), 4.17 (s, 2H), 2.06 (d, J = 1.1 Hz, 3H). 13C NMR (201 MHz, CDCl3) δ 202.9, 162.6, 143.0, 134.8, 133.4, 128.8, 127.6, 126.9, 120.3, 116.9, 105.1, 96.6, 60.9, 48.9, 17.0 Electrospray ionization high-resolution mass spectrometry calculated: C 17 H 18 NO2 + [M+H] + 268.1332, found: 268.1334. HPLC analysis: 94% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 8.150 min (minor peak), 8.753 min (major peak).

[0107] 4ap ((R)-1-(2-(Hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)-3-methoxypyridin-2(1H)-one) was prepared using the general procedure described above in 96% yield (27.2 mg) with 94% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 13.2 ( c 1.34, dichloromethane); 1H NMR (800 MHz, CDCl3) δ 7.29 (t, J = 7.6 Hz, 2H), 7.25 – 7.20 (m, 3H), 6.95 (dd, J = 6.9, 1.7 Hz, 1H), 6.68 (dd, J = 7.4, 1.7 Hz, 1H), 6.29 (q, J =2.0 Hz, 1H), 6.21 (t, J = 7.1 Hz, 1H), 4.78 (ddd, J = 78.8, 14.1, 1.9 Hz,2H), 4.50 (s, 1H), 4.22 – 4.13 (m, 2H), 3.84 (s, 3H). 13 C NMR (201 MHz, CDCl3): 203.0, 158.6, 149.9, 133.3, 128.8, 128.1, 127.5, 127.0, 113.1, 106.5, 104.9,96.7, 61.0, 56.0, 48.9. ESI-HRMS calculated: C 17 H 18 NO3 + [M+H] + 284.1281, found: 284.1272. HPLC analysis: 94% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 11.250 min (minor peak), 12.047 min (major peak).

[0108] 4aq ((R)-1-(2-(Hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)-4-methoxypyridin-2(1H)-one) was prepared according to the general procedure described above in 93% yield (26.3 mg) with 97% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 43.8 ( c 0.85, dichloromethane); 1 H NMR (600 MHz, CDCl3) δ 7.32 – 7.15 (m, 6H), 6.29 (s, 1H), 6.03 –5.97 (m, 1H), 5.96 (d,J = 3.1 Hz, 1H), 4.79 – 4.60 (m, 3H), 4.17 (s, 2H), 3.78 (d, J = 2.3 Hz, 3H). 13 C NMR (201 MHz, CDCl3) δ 202.7, 168.7, 164.8,137.2, 133.4, 128.8, 127.5, 126.9, 105.1, 102.4, 97.1, 96.7, 60.9, 55.7,48.1. Electrospray ionization high-resolution mass spectrometry calculated: C 17 H 18 NO3 + [M+H] + 284.1281, found: 284.1273. HPLC analysis: 97% ee (AS-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 23.857 min (minor peak), 30.583 min (major peak).

[0109] 4ar((R)-1-(2-(Hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)-5-methoxypyridin-2(1H)-one) was prepared using the general procedure described above in 98% yield (27.7 mg) with 97% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 95.7 ( c 0.70,CHCl3); 1 H NMR (800 MHz, CDCl3) δ 7.35 – 7.18 (m, 6H), 6.75 (d, J = 3.2 Hz,1H), 6.62 (d, J = 9.8 Hz, 1H), 6.33 (t, J = 2.0 Hz, 1H), 4.73 (ddd, J =215.3, 14.0, 1.9 Hz, 3H), 4.18 (d, J = 2.1 Hz, 2H), 3.58 (s, 3H). 13C NMR (201 MHz, CDCl3) δ 202.9, 161.1, 144.34, 134.8, 133.4, 128.8, 127.6, 126.9, 121.5,117.6, 104.9, 96.6, 60.8, 56.4, 49.4. ESI-HRMS calculated: C 17 H 18 NO3 + [M+H] + 284.1281, found: 284.1273. HPLC analysis: 97% ee (AD-H, 15% isopropanol / n-hexane, 1.0 ml / min, UV: 254 nm), t R = 9.143 min (minor peak), 9.540 min (major peak).

[0110] 4as ((R)-1-(2-(Hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)-2-oxo-1,2-dihydropyridine-3-carbonitrile) was prepared using the general procedure described above in 98% yield (27.2 mg) with 94% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 47.0 ( c 1.17, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.78 (dd, J = 7.2, 2.0 Hz, 1H), 7.62 (dd, J =6.7, 2.0 Hz, 1H), 7.28 (t, J = 7.5 Hz, 2H), 7.20 (dd, J = 23.1, 7.5 Hz, 3H),6.32 (t, J = 2.4 Hz, 1H), 6.28 (t, J = 6.9 Hz, 1H), 4.79 (ddd, J = 55.2,14.5, 2.4 Hz, 2H), 4.27 (t, J = 2.2 Hz, 2H), 3.54 (s, 1H). 13C NMR (201 MHz,CDCl3) δ 202.7, 160.1, 147.5, 143.1, 132.7, 128.9, 127.9, 127.0, 115.4,106.2, 105.6, 105.0, 98.7, 61.5, 49.3. ESI-HRMS calculated: C 17 H 15 N2O2 + [M+H] + 279.1128, found: 279.1119. HPLC analysis: 94% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 12.240 min (minor peak), 12.860 min (major peak).

[0111] 4at ((R)-1-(2-(Hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)-6-oxo-1,6-dihydropyridine-3-carbonitrile) was prepared using the general procedure described above in 96% yield (26.7 mg) with 93% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 178.0 ( c 0.75, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.84 (d, J = 2.5 Hz, 1H), 7.37 (dd, J = 9.5,2.5 Hz, 1H), 7.31 (t, J = 7.6 Hz, 2H), 7.25 – 7.20 (m, 3H), 6.59 (d, J = 9.5Hz, 1H), 6.36 (t, J = 2.3 Hz, 1H), 4.84 – 4.69 (m, 2H), 4.26 (s, 2H), 3.21(s, 1H). 13 C NMR (201 MHz, CDCl3) δ 202.7, 161.3, 145.0, 139.3, 132.5, 128.9,128.1, 127.0, 121.6, 115.8, 104.83, 98.9, 92.2, 61.5, 49.0. Electrospray ionization high-resolution mass spectrometry C17 H 15 N2O2 + [M+H] + 279.1128, found: 279.1129. HPLC analysis: 93% ee (IA, 15%, 1.0 ml / min, UV: 254 nm), t R = 12.407 min (minor peak), 13.183 min (major peak).

[0112] 4au ((R)-1-(2-(Hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)-3-(trifluoromethyl)pyridin-2(1H)-one) was prepared using the general procedure described above in 96% yield (30.8 mg) with 95% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 337.0 ( c 0.70, dichloromethane); 1 H NMR (600 MHz, CDCl3) δ 7.75 (d, J = 7.1 Hz, 1H), 7.53 (d, J =6.7 Hz, 1H), 7.34 – 7.15 (m, 5H), 6.33 (s, 1H), 6.27 (t, J = 7.0 Hz, 1H), 4.91 – 4.66 (m, 2H), 4.26 (s, 2H), 3.56 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ202.9, 158.9, 141.5, 139.4 (q, J = 5.0 Hz), 132.9, 128.8, 127.8, 126.9,123.2, 122.5 (q, J = 271.4 Hz), 120.7 (q, J = 31.2 Hz), 105.1, 98.2, 61.5,48.9. 19 F NMR (376 MHz, CDCl3) δ -66.0. Electrospray ionization high-resolution mass spectrometry calculated: C 17 H 14 F3NNaO2 + [M+Na] +344.0869, found: 344.0871. HPLC analysis: 95% ee (IA, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 6.943 min (minor peak), 7.290 min (major peak).

[0113] 4av ((R)-1-(2-(Hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)-5-(trifluoromethyl)pyridin-2(1H)-one) was prepared using the general procedure described above in 96% yield (30.8 mg) with 94% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 87.8 ( c 0.60, dichloromethane); 1 H NMR (600 MHz, CDCl3) δ 7.71 (s, 1H), 7.47 (dd, J = 9.6, 2.5 Hz,1H), 7.30 (t, J = 7.6 Hz, 2H), 7.23 (dd, J = 12.2, 7.4 Hz, 3H), 6.67 (d, J =9.6 Hz, 1H), 6.36 (t, J = 2.4 Hz, 1H), 4.77 (ddd, J = 62.9, 14.3, 2.1 Hz,2H), 4.24 (s, 2H), 3.50 (d, J = 6.9 Hz, 1H). 13 C NMR (201 MHz, CDCl3) δ 202.9,162.4, 137.0 (q, J = 5.2 Hz), 135.7, 132.7, 128.9, 127.9, 126.9, 123.7 (q, J = 270.3 Hz), 121.4, 110.9 (q, J = 35.2 Hz), 104.9, 98.2, 61.2, 49.1. 19 F NMR (376 MHz, CDCl3) δ -62.5. Electrospray ionization high-resolution mass spectrometry calculated value: C 17 H 14F3NNaO2 + [M+Na] + 344.0869, found: 344.0876. HPLC analysis: 94% ee (AS-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 15.107 min (minor peak), 11.920 min (major peak).

[0114] 4aw ((R)-1-(2-(Hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)-6-oxo-1,6-dihydropyridine-3-carbaldehyde) was prepared using the general procedure described above in 98% yield (27.5 mg) with 93% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 175.0 ( c 0.70, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 9.49 (d, J = 0.8 Hz, 1H), 7.92 (d, J =2.5 Hz, 1H), 7.79 (dd, J = 9.5, 2.5 Hz, 1H), 7.33 – 7.15 (m, 5H), 6.62 (d, J = 9.4 Hz, 1H), 6.35 (t, J = 2.3 Hz, 1H), 4.91 – 4.76 (m, 2H), 4.28 (d, J =2.3 Hz, 2H), 3.44 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 202.7, 185.9, 162.9,146.5, 136.3, 132.7, 128.9, 128.0, 127.0, 120.9, 118.89, 105.1, 98.7, 61.5,48.9. ESI-HRMS calculated: C 17 H 16 NO3 + [M+H] +282.1125, found: 282.1120. HPLC analysis: 93% ee (AS-H, 10% isopropanol / n-hexane, 1.0 ml / min, UV: 254 nm), t R = 69.843 min (minor peak), 55.357 min (major peak).

[0115] 4ax ((R)-1-(2-(Hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)-5-nitropyridin-2(1H)-one) was prepared using the general procedure described above in 98% yield (29.2 mg) with 93% ee. Purification by flash silica gel column chromatography (50% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 63.1 ( c 1.25, CHCl3); 1 HNMR (800 MHz, CDCl3) δ 8.65 (d, J = 3.1 Hz, 1H), 8.02 (dd, J = 10.0, 3.0 Hz,1H), 7.33 – 7.14 (m, 5H), 6.54 (d, J = 10.0 Hz, 1H), 6.36 (p, J = 2.4 Hz,1H), 4.90 – 4.72 (m, 2H), 4.29 (d, J = 2.4 Hz, 2H), 3.18 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 202.5, 161.8, 139.5, 133.6, 132.4, 128.9, 128.1, 127.0, 119.5,104.9, 99.3, 61.6, 49.3. Electrospray ionization high-resolution mass spectrometry calculated: C 16 H 14 N2NaO4 + [M+Na] + 321.0846, found: 321.0845. HPLC analysis: 93% ee (IB, 10% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 27.210 min (minor peak), 27.707 min (major peak).

[0116] 4ay ((R)-1-(2-(Hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)-5-phenylpyridin-2(1H)-one) was prepared using the general procedure described above in 98% yield (32.2 mg) with 95% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 118.1 ( c 1.22, dichloromethane); 1 H NMR (600 MHz, CDCl3) δ 7.66 (dd, J = 9.4, 2.5 Hz, 1H), 7.51 (d, J =2.6 Hz, 1H), 7.37 – 7.19 (m, 10H), 6.72 (d, J = 9.4 Hz, 1H), 6.34 (t, J = 2.3Hz, 1H), 4.91 – 4.73 (m, 2H), 4.47 (s, 1H), 4.24 (s, 2H). 13 C NMR (201 MHz,CDCl3) δ 203.0, 162.5, 140.2, 136.0, 134.7, 133.3, 129.1, 128.8, 127.7,127.6, 127.0, 125.9, 121.8, 120.7, 105.2, 97.2, 61.1, 49.1. ESI-HRMS calculated: C 22 H 20 NO2 + [M+H] + 330.1489, found: 330.1483. HPLC analysis: 95% ee (IA, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 10.520 min (minor peak), 11.033 min (major peak).

[0117] 4az ((R)-methyl 1-(2-(hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)-6-oxo-1,6-dihydropyridine-3-carboxylate) was prepared using the general procedure described above in 98% yield (30.4 mg) with 93% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D= 179.7( c 1.15, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 8.20 (d, J = 2.5 Hz, 1H), 7.85(dd, J = 9.5, 2.5 Hz, 1H), 7.33 – 7.12 (m, 5H), 6.56 (d, J = 9.5 Hz, 1H),6.33 (t, J = 2.3 Hz, 1H), 4.88 – 4.72 (m, 2H), 4.24 (d, J = 2.3 Hz, 2H), 3.81(s, 3H), 3.74 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 202.7, 164.4, 163.0, 142.8,139.2, 132.9, 128.8, 127.7, 127.0, 119.7, 110.8, 105.1, 105.1, 98.3, 61.3,52.2, 49.0. ESI-HRMS calculated: C 18 H 18 NO4 + [M+H] + 312.1230, found: 312.1226. HPLC analysis: 93% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 10.603 min (minor peak), 11.320 min (major peak).

[0118] 4aaa ((R)-1-(2-(Hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)-4-methoxy-2-oxo-1,2-dihydropyridine-3-carbonitrile) was prepared using the general procedure described above in 98% yield (30.2 mg) with 92% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 65.2( c 0.25, CHCl3); 1 H NMR (800 MHz, DMSO- d 6) δ 8.06 (d, J= 7.8 Hz, 1H), 7.32 –7.12 (m, 5H), 6.37 (d, J = 7.8 Hz, 1H), 6.35 (t, J = 2.9 Hz, 1H), 5.25 (t, J = 5.9 Hz, 1H), 4.67 (ddd, J = 56.0, 15.1, 3.2 Hz, 2H), 4.11 (dd, J = 6.0, 2.4Hz, 2H), 3.89 (s, 3H). 13 C NMR (201 MHz, DMSO) δ 201.2, 173.1, 160.7, 146.2, 134.2, 129.0, 127.7, 127.3, 115.0, 107.5, 98.8, 94.3, 86.4, 61.0, 58.1, 47.6. ESI-HRMS calculated: C 18 H 16 N2NaO3 + [M+Na] + 331.1053, found: 331.1047. HPLC analysis: 92% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 19.447 min (minor peak), 21.100 min (major peak).

[0119] 4aab ((R)-1'-(2-(Hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)-[2,3'-bipyridyl]-6'(1'H)-one) was prepared according to the general procedure described above in 98% yield (32.3 mg) with 94% ee. Purification by flash silica gel column chromatography (50% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 119.2 ( c 0.90, dichloromethane); 1 H NMR (400 MHz, CDCl3) δ 8.57 (dd, J = 5.0, 1.7 Hz, 1H), 8.19 (d, J = 2.6 Hz, 1H), 8.02 (dd, J = 9.5, 2.6 Hz, 1H), 7.69 (td,J = 7.7, 1.9 Hz,1H), 7.42 (d, J = 7.9 Hz, 1H), 7.30 – 7.16 (m, 6H), 6.73 (d, J = 9.5 Hz, 1H),6.35 (t, J = 2.1 Hz, 1H), 4.96 – 4.76 (m, 2H), 4.34 – 4.25 (m, 1H), 4.22 (s, 2H). 13 C NMR (201 MHz, CDCl3) δ 203.0, 163.0, 152.9, 149.7, 138.6, 137.0,136.6, 133.3, 128.8, 127.6, 127.0, 122.1, 120.3, 120.0, 118.5, 105.0, 97.2,61.0, 49.2. ESI-HRMS calculated: C 21 H 19 N2O + [M+H] + 331.1441, found: 331.1435. HPLC analysis: 94% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 13.057 min (minor peak), 14.503 min (major peak).

[0120] 4aac ((R)-1-(2-(Hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)-2-methyl-6-oxo-1,6-dihydro-[3,4-bipyridine]-5-carbonitrile) was prepared using the general procedure described above in 98% yield (36.3 mg) and 97% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a white solid. MP = 88-90°C; [α] 25 D = 231.2 ( c 1.17, dichloromethane); 1 H NMR (600 MHz, CDCl3) δ 8.59 (d, J =4.9 Hz, 2H), 7.58 (d, J = 2.1 Hz, 1H), 7.32 – 7.13 (m, 5H), 6.85 (d, J= 4.8Hz, 2H), 6.32 (t, J = 2.7 Hz, 1H), 5.03 (dd, J = 126.1, 15.5 Hz, 2H), 4.37(d, J = 2.4 Hz, 2H), 3.55 (s, 1H), 2.40 (s, 3H). 13 C NMR (201 MHz, CDCl3) δ201.6, 160.1, 151.2, 150.3, 146.8, 144.9, 132.6, 128.9, 128.0, 126.9, 124.2,118.5, 115.3, 104.9, 102.2, 99.4, 61.7, 44.6, 18.7. ESI-HRMS calculated: C 23 H 20 N3O2 + [M+H] + 370.1550, found: 370.1547. HPLC analysis: 97% ee (AD-H, 15% isopropanol / n-hexane 1.0 ml / min, UV: 254 nm), t R = 22.503 min (minor peak), 19.917 min (major peak).

[0121] The reaction results of the allenyl dimethylene cyclic carbonate compound and the nitrogen-containing heterocyclic substrate include the following compounds 5aa to 5a1.

[0122] Following the general procedure described above, 5aa ((R)-1-(2-(Hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)pyrazin-2(1H)-one) was prepared in 98% yield (24.9 mg) with 96% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D =201.3 ( c 0.60, CHCl3); 1 H NMR (600 MHz, CDCl3) δ 8.18 (s, 1H), 7.40 – 7.27 (m, 3H), 7.24 – 7.11 (m, 4H), 6.35 (t, J = 2.4 Hz, 1H), 4.78 – 4.61 (m, 2H), 4.24 (d, J= 2.4 Hz, 2H), 3.61(s, 1H). 13 C NMR (201 MHz, CDCl3) δ 202.9, 156.5, 149.4, 132.7, 128.88,128.86, 128.5, 127.9, 127.0, 124.8, 104.3, 98.2, 61.3, 61.3, 48.4. ESI-HRMS calculated: C 15 H 15 N2O2 + [M+H] + 255.1128, found: 255.1118. HPLC analysis: 96% ee (AS-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 21.540 min (minor peak), 15.140 min (major peak).

[0123] 5ab ((R)-3-(2-(Hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)pyrimidin-4(3H)-one) was prepared using the general procedure described above in 98% yield (24.9 mg) with 92% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 94.6 ( c 1.447, dichloromethane); 1 HNMR (600 MHz, CDCl3) δ 8.15 (s, 1H), 7.86 (d, J = 6.6 Hz, 1H), 7.31 – 7.25(m, 2H), 7.24 – 7.15 (m, 3H), 6.45 (dd, J = 6.6, 1.0 Hz, 1H), 6.33 (t, J =2.3 Hz, 1H), 4.83 – 4.61 (m, 2H), 4.27 (q, J = 2.5 Hz, 2H), 3.64 (t, J = 6.4Hz, 1H). 13C NMR (201 MHz, CDCl3) δ 202.5, 161.4, 153.8, 151.3, 132.7, 128.8,128.8, 127.9, 127.0, 115.8, 105.1, 98.8, 61.5, 45.6. ESI-HRMS calculated: C 15 H 15 N2O2 + [M+H] + 255.1128, found: 255.1132. HPLC analysis: 92% ee (AD-H, 15% isopropanol / n-hexane, 1.0 ml / min, UV: 254 nm), t R = 10.607 min (minor peak), 11.353 min (major peak).

[0124] Following the general procedure described above, 5ac ((R)-1-(2-(hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)-3-methylpyrimidine-2,4(1H,3H)-dione) was prepared in 97% yield (27.5 mg) with 90% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 35.5 ( c 0.73, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.32 – 7.29 (m, 2H), 7.25 – 7.20 (m, 3H),7.16 (d, J = 7.9 Hz, 1H), 6.36 (p, J = 2.3 Hz, 1H), 5.74 (d, J = 7.9 Hz, 1H),4.55 (ddd, J = 114.5, 15.1, 2.4 Hz, 2H), 4.27 (d, J = 2.3 Hz, 2H), 3.31 (d, J = 23.5 Hz, 3H), 2.72 (s, 1H). 13C NMR (201 MHz, CDCl3) δ 202.4, 163.0, 152.1,141.9, 132.8, 128.8, 127.9, 127.0, 104.9, 102.2, 98.7, 61.5, 48.4, 27.9. ESI-HRMS calculated: C 16 H 16 N2NaO + [M+Na] + 307.1053, found: 307.1062. HPLC analysis: 90% ee (AS-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 24.667 min (minor peak), 21.710 min (major peak).

[0125] 5ad ((R)-2-(2-(Hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)isoquinolin-1(2H)-one) was prepared according to the general procedure described above in 55% yield (16.7 mg) with 96% ee. Purification by flash silica gel column chromatography (50% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = -11.6 ( c 0.50, dichloromethane); 1 HNMR (600 MHz, CDCl3) δ 8.46 (d, J = 8.0 Hz, 1H), 7.68 (t, J = 7.6 Hz, 1H),7.54 (d, J = 8.1 Hz, 2H), 7.30 – 7.22 (m, 5H), 7.11 (d, J = 7.4 Hz, 1H), 6.59(d, J = 7.3 Hz, 1H), 6.32 (s, 1H), 4.96 – 4.73 (m, 2H), 4.31 (s, 1H), 4.19(s, 2H). 13 C NMR (201 MHz, CDCl3) δ 202.8, 163.1, 137.1, 133.5, 132.7, 131.0,128.8, 128.1, 127.5, 127.3, 127.0, 126.1, 125.7, 107.8, 104.9, 96.6, 61.0,48.5. ESI-HRMS calculated: C 20 H 17 NNaO2 + [M+Na] + 326.1151, found: 326.1153. HPLC analysis: 96% ee (IB, 10% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 14.423 min (minor peak), 15.347 min (major peak).

[0126] 5ae ((R)-5-(2-(Hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)furo[3,2-c]pyridin-4(5H)-one) was prepared according to the general procedure described above in 96% yield (28.1 mg) with 96% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 25.8 ( c 0.55, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.53 (d, J = 2.1 Hz, 1H), 7.33 – 7.17 (m,6H), 7.01 (d, J = 2.0 Hz, 1H), 6.63 (d, J = 7.3 Hz, 1H), 6.31 (q, J = 2.1 Hz,1H), 4.84 (ddd, J = 73.0, 14.4, 1.9 Hz, 2H), 4.36 (s, 1H), 4.27 – 4.12 (m,2H). 13C NMR (201 MHz, CDCl3) δ 202.8, 160.1, 159.7, 144.0, 133.6, 133.7,128.8, 127.6, 127.0, 126.9, 116.2, 107.4, 105.2, 97.4, 96.9, 61.0, 48.2. ESI-HRMS calculated: C 18 H 16 NO3 + [M+H] + 294.1125, found: 294.1133. HPLC analysis: 96% ee (AS-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 14.250 min (minor peak), 12.090 min (major peak).

[0127] 5af ((R)-5-(2-(Hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)thieno[3,2-c]pyridin-4(5H)-one) was prepared using the general procedure described above in 90% yield (28.0 mg) with 96% ee. Purification by flash silica gel column chromatography (50% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 9.4 ( c 0.70, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.68 (d, J = 5.3 Hz, 1H), 7.34 (d, J = 5.3 Hz,1H), 7.30 – 7.17 (m, 6H), 6.78 (d, J = 7.1 Hz, 1H), 6.32 (q, J = 2.1 Hz, 1H),4.84 (ddd, J = 82.9, 14.3, 1.9 Hz, 2H), 4.43 – 4.35 (m, 1H), 4.20 (t, J = 2.1Hz, 2H). 13C NMR (201 MHz, CDCl3) δ 202.9, 159.8, 148.0, 133.4, 131.6, 130.5,128.8, 127.6, 127.0, 125.3, 125.2, 105.1, 103.5, 96.7, 61.0, 48.3. ESI-HRMS calculated: C 18 H 17 NO2S + [M+H] + 311.0975, found: 311.0975. HPLC analysis: 96% ee (AS-H, 15% isopropanol / n-hexane, 1.0 ml / min, UV: 254 nm), t R = 15.970 min (minor peak), 13.000 min (major peak).

[0128] Following the general procedure described above, 5ag ((R)-1-(2-(Hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)quinoxalin-2(1H)-one) was prepared in 98% yield (29.8 mg) with 92% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 73.1 ( c 1.34, dichloromethane); 1 HNMR (600 MHz, CDCl3) δ 8.34 (s, 1H), 7.90 (d, J = 8.0 Hz, 1H), 7.48 – 7.34(m, 3H), 7.28 – 7.10 (m, 5H), 6.33 (s, 1H), 5.08 (dd, J = 132.1, 15.1 Hz,2H), 4.20 (s, 2H), 3.69 (t, J = 7.0 Hz, 1H). 13 C NMR (201 MHz, CDCl3) δ 203.0, 155.5, 149.5, 133.9, 132.7, 132.1, 131.3, 130.7, 128.7, 127.7, 127.2, 124.3, 114.8, 103.0, 97.9, 61.1, 41.9. ESI-HRMS calculated: C 19 H 16 N2NaO2+ [M+Na] + 327.1104, found: 327.1112. HPLC analysis: 92% ee (IA, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 11.440 min (minor peak), 10.860 min (major peak).

[0129] Following the general procedure above, 5ah ((R)-1-(2-(hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)-3-methylquinoxalin-2(1H)-one) was prepared in 95% yield (30.3 mg) with 92% ee. Purification by flash silica gel column chromatography (50% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 85.0 ( c 1.91, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.82 (dd, J = 7.9, 1.6 Hz, 1H), 7.40 – 7.33 (m, 3H), 7.26 – 7.10 (m, 5H), 6.31 (t, J = 2.2 Hz, 1H), 5.22 – 4.95 (m, 2H), 4.19 (t, J = 4.6 Hz, 2H), 3.86 (t, J = 7.0 Hz, 1H), 2.60 (s, 3H). 13 C NMR (201 MHz,CDCl3) δ 203.0, 157.8, 155.7, 133.2, 132.8, 132.1, 129.9, 129.7, 128.6,127.7, 127.2, 124.2, 114.6, 103.1, 97.6, 61.1, 42.2, 21.5. ESI-HRMS calculated: C 20 H 20 N2O2 + [M+H] + 320.1519, found: 320.1511. HPLC analysis: 92% ee (AD-H, 15% isopropanol / n-hexane, 1.0 ml / min, UV: 254 nm), t R = 9.567 min (minor peak), 8.047 min (major peak).

[0130] Following the general procedure described above, 5ai ((R,E)-3-(4-(dimethylamino)phenylvinyl)-1-(2-(hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)quinoxalin-2(1H)-one) was prepared in 80% yield (36.0 mg) with 99% ee. Purification by flash silica gel column chromatography (30% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 22.2 ( c 0.50, CHCl3); 1 H NMR (800 MHz, CDCl3) δ 8.09 (d, J = 15.9Hz, 1H), 7.86 (dd, J = 7.9, 1.5 Hz, 1H), 7.66 – 7.55 (m, 3H), 7.39 – 7.18 (m,8H), 6.79 – 6.67 (m, 2H), 6.37 (t, J = 2.1 Hz, 1H), 5.25 (d, J = 15.0 Hz,1H), 5.01 (d, J = 15.0 Hz, 1H), 4.17 (s, 2H), 3.99 (s, 1H), 3.04 (s, 6H). 13 CNMR (201 MHz, CDCl3) δ 203.3, 155.9, 152.6, 151.3, 139.2, 134.4, 132.9,131.4, 129.7, 129.6, 129.0, 128.7, 127.6, 127.3, 124.5, 124.3, 116.6, 114.6,112.0, 103.0, 97.1, 61.0, 42.4, 40.2. ESI-HRMS calculated: C 29 H 28 N3NaO2 + [M+Na] + 473.2074, found: 473.2086. HPLC analysis: 99% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 31.817 min (main peak).

[0131] 5aj ((R)-1-(2-(Hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)indole-2,3-dione) was prepared using the general procedure described above in 90% yield (27.5 mg) with 90% ee. Purification by flash silica gel column chromatography (40% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 125.0 ( c 1.03, dichloromethane); 1 HNMR (600 MHz, CDCl3) δ 7.57 (dd, J = 7.4, 1.3 Hz, 1H), 7.48 (td, J = 7.8, 1.4Hz, 1H), 7.25 – 7.06 (m, 6H), 6.93 (d, J = 7.9 Hz, 1H), 6.35 (t, J = 2.4 Hz,1H), 4.67 – 4.44 (m, 2H), 4.28 (s, 2H), 2.49 (s, 1H). 13 C NMR (201 MHz, CDCl3)δ 202.6, 182.9, 158.6, 150.3, 138.3, 132.7, 128.7, 127.8, 127.2, 125.5,124.1, 117.7, 111.1, 102.8, 98.6, 61.4, 39.8. Electrospray ionization high-resolution mass spectrometry C 19 H 16 NO3 + [M+H] + 306.1125, 306.1120. HPLC 90% ee (AD-H, 10%, 1.0 mL / min, UV: 254 nm), t R = 23.213 min (minor peak), 27.440 min (major peak).

[0132] 5ak ((R)-3-(2-(Hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)benzo[d]oxazol-2(3H)-one) was prepared using the general procedure described above in 86% yield (25.3 mg) with 86% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 121.0 ( c1.07, dichloromethane); 1 H NMR (600 MHz, CDCl3) δ 7.38 – 7.06 (m, 8H), 7.04 – 6.90 (m, 1H), 6.35(d, J = 3.4 Hz, 1H), 4.78 – 4.54 (m, 2H), 4.27 (s, 2H), 2.75 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 202.5, 155.1, 142.8, 132.8, 130.6, 128.7, 128.7, 127.7,127.21, 127.19, 124.0, 122.8, 110.2, 109.1, 103.3, 98.2, 61.2, 41.7. ESI-HRMS calculated: C 18 H 15 NO3 + [M+Na] + 316.0944, found: 316.0948. HPLC analysis: 86% ee (IA, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 8.557 min (minor peak), 8.983 min (major peak).

[0133] 5al ((R)-3-(2-(Hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)benzo[d]thiazol-2(3H)-one) was prepared using the general procedure described above in 98% yield (30.3 mg) with 88% ee. Purification by flash silica gel column chromatography (60% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 125.0 ( c 1.03, dichloromethane); 1H NMR (600 MHz, CDCl3) δ 7.42 (d, J = 7.8 Hz, 1H), 7.27 – 7.14 (m, 7H), 7.08(d, J = 8.0 Hz, 1H), 6.34 (s, 1H), 4.77 (dd, J = 94.0, 15.3 Hz, 2H), 4.22 (s, 2H), 3.04 (s, 1H). 13C NMR (201 MHz, CDCl3) δ 202.6, 171.2, 136.6, 132.9,128.68, 128.66, 127.6, 127.2, 126.6, 123.6, 122.7, 122.7, 111.6, 103.1, 97.8,61.1, 42.2. ESI-HRMS calculated: C 18 H 15 NO2S + [M+Na] + 332.0716, found: 332.0718. HPLC analysis: 88% ee (IA, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 7.863 min (minor peak), 8.667 min (major peak).

[0134] Example 3

[0135] like Figure 6 Under argon, allenyl dimethylene cyclic carbonate compound 1a (0.15 mmol), secondary amine substrate 7 (0.10 mmol), palladium catalyst (Pd2(dba)3•CHCl3) (5 mol%, 0.005 mmol) and ligand (L1:(1R,2R)-(+)-1,2-diaminocyclohexane-N,N'-bis(2-phenylphosphino-1-naphthoyl)) (11 mol%, 0.011 mmol) were weighed into a Schlenk tube. 1 mL of dichloromethane was added, and the reaction was stirred continuously at room temperature. After completion of the reaction, monitored by thin-layer chromatography, the resulting axially chiral allene product 8 was purified by flash silica gel column chromatography using an eluent of ethyl acetate / petroleum ether (1 / 6). The yield was calculated by weight, and the ee value was determined using high-performance liquid chromatography coupled with a chiral column.

[0136] The reaction results of the allenyl dimethylene cyclic carbonate compound and the secondary amine include the following compounds 8aa to 8ag.

[0137] 8aa ((R)-2-((Benzyl(methyl)amino)methyl)-4-phenylbuta-2,3-dien-1-ol) was prepared according to the general procedure described above in 73% yield (20.4 mg) with 90% ee. Purification by flash silica gel column chromatography (20% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 30.5 ( c 0.60, dichloromethane); 1H NMR (400MHz, CDCl3) δ 7.44 – 7.10 (m, 10H), 6.23 (s, 1H), 4.37 (d, J = 2.0 Hz, 2H),3.61 (s, 2H), 3.29 (d, J = 2.0 Hz, 2H), 2.31 (s, 3H). 13 C NMR (201 MHz, CDCl3)δ 203.1, 137.8, 134.2, 129.2, 128.73, 128.70, 128.6, 128.5, 1275, 127.2,126.93, 126.91, 103.4, 95.1, 65.2, 62.1, 60.2, 42.1. ESI-HRMS calculated: C 19 H 22 NO + [M+H] + 280.1696, found: 280.1687. HPLC analysis: 90% ee (OD-H, 10% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 7.250 min (minor peak), 9.483 min (major peak).

[0138] 8ab((R)-2-((Benzyl(cyclohexyl)amino)methyl)-4-phenylbuta-2,3-dien-1-ol) was prepared according to the general procedure described above in 58% yield (20.1 mg) with 94% ee. Purification by flash silica gel column chromatography (20% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 106.0 ( c 0.70, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.39 – 7.23 (m, 10H), 6.19 (d, J = 2.0 Hz, 1H), 4.81 (s,1H), 4.32 – 4.19 (m, 2H), 3.67 (d, J = 56.0 Hz, 2H), 3.38 (s, 2H), 2.80 –2.74 (m, 1H), 1.87 – 1.77 (m, 4H), 1.66 – 1.61 (m, 1H), 1.39 – 1.09 (m, 5H).13 C NMR (201 MHz, CDCl3) δ 203.2, 139.4, 134.3, 129.0, 128.7, 128.6, 127.2,127.1, 126.9, 104.0, 94.8, 65.0, 57.6, 53.8, 52.5, 28.3, 27.6, 26.4, 26.2,26.0. ESI-HRMS calculated: C 24 H 30 NO + [M+H] + 348.2322, found: 348.2327. HPLC analysis: 94% ee (IB, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 4.170 min (minor peak), 4.513 min (major peak).

[0139] 8ac ((R)-2-((allyl(benzyl)amino)methyl)-4-phenylbuta-2,3-dien-1-ol) was prepared using the general procedure described above in 60% yield (18.3 mg) with 90% ee. Purification by flash silica gel column chromatography (20% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 61.3 ( c 1.06, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.44 – 7.16 (m, 10H), 6.22 (q, J = 2.0 Hz, 1H), 5.90 (ddt, J = 18.3, 9.7, 6.5 Hz, 1H), 5.33 – 5.09 (m, 2H), 4.62 (s, 1H), 4.40 – 4.25(m, 2H), 3.67 (s, 2H), 3.41 – 3.25 (m, 2H), 3.18 (dd, J = 6.5, 1.5 Hz, 2H). 13C NMR (201 MHz, CDCl3) δ 203.2, 138.0, 134.4, 134.2, 129.2, 128.7, 128.6,127.4, 127.2, 126.9, 119.0, 103.7, 95.2, 64.9, 57.9, 56.2, 56.0. ESI-HRMS calculated: C 21 H 24 NO + [M+H] + 306.1852, found: 306.1854. HPLC analysis: 90% ee (IB, 15% isopropanol / n-hexane, 1.0 ml / min, UV: 254 nm), t R = 4.380 min (minor peak), 4.840 min (major peak).

[0140] 8ad ((R)-2-((dibenzylamino)methyl)-4-phenylbuta-2,3-dien-1-ol) was prepared according to the general procedure described above in 81% yield (28.8 mg) with 81% ee. Purification by flash silica gel column chromatography (20% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 26.5 ( c 1.03, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.42 – 7.08 (m, 15H), 6.26 (p, J = 2.2 Hz, 1H), 4.28 (d, J = 2.2 Hz,2H), 4.02 (s, 1H), 3.65 (d, J = 2.0 Hz, 4H), 3.36 – 3.21 (m, 2H). 13 C NMR (201 MHz, CDCl3) δ 203.0, 138.2, 134.2, 129.2, 128.7, 128.59, 128.57, 127.4,127.2, 126.9, 104.3, 95.7, 64.3, 58.2, 55.6. ESI-HRMS calculated: C 25 H 26 NO + [M+H] +356.2009, found: 356.2009. HPLC analysis: 81% ee (IB, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 4.770 min (minor peak), 5.153 min (major peak).

[0141] 8ae ((R)-2-((methyl((S)-1-phenylethyl)amino)methyl)-4-phenylbuta-2,3-dien-1-ol) was prepared according to the general procedure described above in 56% yield (16.4 mg) with 90% ee. Purification by flash silica gel column chromatography (20% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = -40.9 ( c 0.85, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.38 – 7.13 (m, 10H), 6.21 (p, J = 1.9 Hz, 1H), 4.39– 4.22 (m, 2H), 3.71 (q, J = 6.7 Hz, 1H), 3.23 (ddd, J = 118.9, 12.6, 2.0 Hz,2H), 2.32 (s, 3H), 1.44 (d, J = 6.8 Hz, 3H). 13 C NMR (201 MHz, CDCl3) δ 203.2, 134.2, 128.68, 128.65, 128.53, 128.50, 128.5, 127.8, 127.5, 127.1, 126.9, 126.9, 103.4, 94.8, 65.3, 63.6, 57.6, 38.1, 18.1 Calcd. by electrospray ionization-high-resolution mass spectrometry: C 20 H 24 NO + [M+H] + 294.1852, found: 294.1843. HPLC analysis: 90% ee (OD-H, 5% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 8.207 min (minor peak), 11.423 min (major peak).

[0142] 8af ((R)-2-(morpholinomethyl)-4-phenylbuta-2,3-dien-1-ol) was prepared according to the general procedure described above in 55% yield (13.5 mg) with 99% ee. Purification by flash silica gel column chromatography (50% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 61.0 ( c 0.86, dichloromethane); 1 H NMR (800 MHz, CDCl3)δ 7.37 – 7.16 (m, 5H), 6.22 (q, J = 2.0 Hz, 1H), 4.78 (s, 1H), 4.38 (t, J =2.1 Hz, 2H), 3.74 (t, J = 4.7 Hz, 4H), 3.27 (dd, J = 3.6, 1.9 Hz, 2H), 2.60(s, 4H). 13 C NMR (201 MHz, CDCl3) δ 203.3, 134.0, 128.7, 127.3, 126.9, 102.1,95.1, 66.9, 65.3, 61.7, 53.5. Electrospray ionization high-resolution mass spectrometry calculated: C 15 H 19 NNaO2 + [M+Na] + 268.1308, found: 268.1316. HPLC analysis: 99% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 6.147 min (main peak).

[0143] 8ag (benzyl (R)-4-(2-(hydroxymethyl)-4-phenylbuta-2,3-dien-1-yl)piperazine-1-carboxylate) was prepared using the general procedure described above in 82% yield (31.0 mg) with 90% ee. Purification by flash silica gel column chromatography (40% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = 86.9 ( c 1.00, dichloromethane); 1 HNMR (800 MHz, CDCl3) δ 7.48 – 7.10 (m, 10H), 6.23 (p, J= 2.0 Hz, 1H), 5.13(d, J = 1.7 Hz, 2H), 4.52 (s, 1H), 4.40 – 4.27 (m, 2H), 3.55 (t, J = 5.3 Hz,4H), 3.26 (t, J = 2.1 Hz, 2H), 2.56 (s, 3H). 13 C NMR (201 MHz, CDCl3) δ 203.3, 155.2, 136.6, 133.9, 128.8, 128.6, 128.1, 128.0, 127.3, 126.9, 102.4, 95.3, 67.3, 65.1, 61.1, 52.8, 43.8. ESI-HRMS calculated: C 23 H 27 N2O + [M+H] + 379.2016, found: 379.2010. HPLC analysis: 90% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 14.607 min (minor peak), 17.113 min (major peak).

[0144] Example 4

[0145] like Figure 7 Under argon, allenyl dimethylene cyclic carbonate compound 1a (0.15 mmol), bis(benzenesulfonic acid) methane 7h (0.10 mmol), palladium catalyst Pd2(dba)3 (5 mol%, 0.005 mmol) and ligand L2: N,N'-[(1R,2R)-1,2-bis(2-methoxy)phenyl-1,2-ethanediyl]bis[2-diphenylphosphinobenzamide] (11 mol%, 0.011 mmol), respectively, were weighed into a Schlenk tube. 1 mL of dichloromethane was added, and the reaction was stirred continuously at room temperature. After completion of the reaction was monitored by thin-layer chromatography, the resulting axially chiral allene product 8ah was purified by flash silica gel column chromatography using an eluent consisting of ethyl acetate / petroleum ether (1 / 4). The yield was calculated by weight, and the ee value was determined using high-performance liquid chromatography (HPLC) with a chiral column.

[0146] The reaction results of the allenyl dimethylene cyclic carbonate compound and bis(benzenesulfonic acid) methane include the following compound 8ah.

[0147] 8ah ((R)-2-(2,2-bis(phenylsulfonyl)ethyl)-4-phenylbuta-2,3-dien-1-ol) was prepared using the general procedure described above in 99% yield (44.9 mg) with 93% ee. Purification by flash silica gel column chromatography (40% ethyl acetate / petroleum ether) afforded a viscous liquid. [α] 25 D = -344.2 ( c 1.11, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 8.01 – 7.18 (m, 15H), 6.32 (q, J = 2.8 Hz, 1H), 4.86 (t, J = 5.4 Hz, 1H), 4.26 – 4.08 (m, 2H), 3.05 (dddd, J = 57.4, 17.3, 5.4, 3.3 Hz, 2H), 1.99 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 200.9, 137.8, 137.5, 134.8,134.5, 133.1, 129.8, 129.5, 129.1, 129.1, 128.9, 128.0, 127.3, 106.2, 100.5,81.7, 63.4, 25.3. ESI-HRMS calculated: C 24 H 22 NaO5S2 + [M+Na] + 477.0801, found: 477.0792. HPLC analysis: 93% ee (OD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 35.780 min (minor peak), 29.173 min (major peak).

[0148] Example 5

[0149] like Figure 8Under argon atmosphere, allenyl dimethylene cyclic carbonate compound 1a (0.10 mmol), sodium arylsulfinate 9 (0.25 mmol), palladium catalyst and ligand tris(dibenzylideneacetone)dipalladium-chloroform adduct (5 mol%, 0.005 mmol) / L3: N,N'-[(1R,2R)-1,2-diphenyl-1,2-ethanediyl]bis[2-diphenylphosphinobenzamide] (11 mol%, 0.011 mmol) were weighed and added to a Shrek tube. 1 ml of 1,2-dichloroethane was added and the mixture was heated to 0.1 ℃. o The reaction was stirred continuously at 400 °C. After completion of the reaction was monitored by thin-layer chromatography, the obtained axially chiral allene product 6 was purified by flash silica gel column chromatography with an eluent consisting of ethyl acetate / petroleum ether in a ratio of 1:3. The yield was calculated by weighing, and the ee value was tested using high-performance liquid chromatography coupled with a chiral column.

[0150] The reaction results of the allenyl dimethylene cyclic carbonate compound and sodium benzenesulfinate include the following compounds 6aa to 6ma and 6ab to 6at.

[0151] Compound 6aa ((S)-4-phenyl-2-((phenylsulfonyl)methyl)buta-2,3-dien-1-ol) was prepared using the general procedure described above in 98% yield (29.4 mg) with 93% ee. Purification by flash chromatography on silica gel (33% ethyl acetate / petroleum ether) afforded a white solid. MP = 78-80°C; [α] 25 D = 209.2 (c 0.50, dichloromethane); 1 H NMR (400 MHz, CDCl3) δ 8.03 – 7.43 (m, 5H), 7.31 – 7.18 (m, 3H), 7.11 –7.03 (m, 2H), 6.08 (td, J = 2.6, 1.3 Hz, 1H), 4.39 (d, J = 2.6 Hz, 2H), 4.01(t, J = 1.6 Hz, 2H), 2.52 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 206.6, 138.1,134.0, 132.4, 129.4, 128.7, 128.4, 127.8, 127.3, 97.8, 97.5, 62.6, 57.4. ESI-HRMS calculated: C 17 H 17 O3S + [M+H] +301.0893, found: 301.0902. HPLC analysis: 93% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 24.143 min (minor peak), 17.787 min (major peak).

[0152] 6ba ((S)-4-(3-fluorophenyl)-2-((phenylsulfonyl)methyl)buta-2,3-dien-1-ol) was prepared according to the general procedure described above in 92% yield (29.2 mg) with 90% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a white solid. MP = 102-104°C; [α] 25 D = 173.7 ( c 0.88, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.98 – 7.53 (m, 5H), 7.27 – 6.58 (m, 4H), 6.07 (t, J = 2.2 Hz, 1H), 4.39 (d, J = 4.3 Hz, 2H), 4.01 (d, J = 1.8 Hz, 2H),2.63 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 206.7, 162.9 (d, J = 246.3 Hz),138.0, 134.9 (d, J = 7.6 Hz), 134.1, 130.1 (d, J = 8.2 Hz), 129.4, 128.3,123.1 (d, J = 2.8 Hz), 114.7 (d, J = 21.4 Hz), 113.8 (d, J = 22.3 Hz), 98.4,96.7 (d, J = 2.9 Hz), 62.4, 57.2 (d, J = 3.9 Hz). 19 F NMR (376 MHz, CDCl3) δ -112.8. Electrospray ionization high-resolution mass spectrometry calculated: C 17 H 15FNaO3S + [M+Na] + 341.0618, found: 341.0624. HPLC analysis: 90% ee (IA, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 24.057 min (minor peak), 16.160 min (major peak).

[0153] 6ca ((S)-4-(4-Fluorophenyl)-2-((phenylsulfonyl)methyl)buta-2,3-dien-1-ol) was prepared according to the general procedure described above in 75% yield (23.9 mg) with 93% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a white solid. MP = 108-110°C; [α] 25 D = 177.9 ( c 0.53, dichloromethane); 1 H NMR (400 MHz, CDCl3) δ 8.03 – 7.40 (m, 5H), 7.14 – 6.88(m, 4H), 6.10 (td, J = 2.6, 1.3 Hz, 1H), 4.38 (d, J = 3.7 Hz, 2H), 4.00 (d, J = 1.7 Hz, 2H), 2.58 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 206.42 (d, J = 1.6Hz), 162.3 (d, J = 247.5 Hz), 138.2, 134.0, 129.4, 128.9 (d, J = 8.2 Hz),128.4, 115.70 (d, J = 22.0 Hz), 98.0, 96.5, 62.6, 57.4. 19 F NMR (376 MHz,CDCl3) δ -113.7. Electrospray ionization high-resolution mass spectrometry calculated value: C 17 H 15 FNaO3S + [M+Na] +341.0618, found: 341.0617. HPLC analysis: 93% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 21.793 min (minor peak), 20.633 min (major peak).

[0154] 6da ((S)-4-(3-chlorophenyl)-2-((phenylsulfonyl)methyl)buta-2,3-dien-1-ol) was prepared according to the general procedure described above in 87% yield (29.1 mg) with 88% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a clear liquid. [α] 25 D = 106.2 ( c 0.25, dichloromethane); 1 H NMR(800 MHz, CDCl3) δ 7.99 – 7.90 (m, 2H), 7.76 – 7.48 (m, 3H), 7.23 – 6.95 (m,4H), 6.04 (dt, J = 2.7, 1.7 Hz, 1H), 4.39 (dd, J = 2.7, 1.3 Hz, 2H), 4.07 –3.91 (m, 2H), 2.50 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 206.7, 138.0, 134.6,134.5, 134.1, 129.9, 129.4, 128.3, 127.9, 127.1, 125.5, 98.4, 96.5, 62.5,57.4. ESI-HRMS calculated: C 17 H 15 ClNaO3S + [M+Na] + 357.0323, found: 357.0328. HPLC analysis: 88% ee (IA, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 36.190 min (minor peak), 17.540 min (major peak).

[0155] Compound 6ea ((S)-4-(4-chlorophenyl)-2-((phenylsulfonyl)methyl)buta-2,3-dien-1-ol) was prepared according to the general procedure described above in 60% yield (19.8 mg) with 91% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a white solid. MP = 126-128°C; [α] 25 D = 242.2 ( c 0.46, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 8.03 – 7.45 (m, 5H), 7.23 – 6.98 (m, 4H), 6.09 (t, J = 2.3 Hz, 1H), 4.39 (dt, J = 5.4, 3.0 Hz, 2H), 4.00 (d, J = 1.7 Hz, 2H), 2.56 (t, J = 6.2 Hz, 1H). 13 C NMR (201 MHz, CDCl3) δ 206.6,138.2, 134.0, 133.5, 131.0, 129.4, 128.9, 128.5, 128.4, 98.2, 96.6, 62.5,57.3. 13 C NMR (201 MHz, CDCl3) δ 206.6, 138.2, 134.0, 133.5, 131.0, 129.4,128.9, 128.5, 128.4, 98.2, 96.6, 62.5, 57.3. ESI-HRMS calculated: C 18 H 18 NaO4S + [M+Na] + 353.0818, found: 353.0811. HPLC analysis: 91% ee (IA, 15% isopropanol / n-hexane, 1.0 ml / min, UV: 254 nm), t R = 22.663 min (minor peak), 19.333 min (major peak).

[0156] Following the general procedure above, 6fa ((S)-2-((phenylsulfonyl)methyl)-4-(o-tolyl)buta-2,3-dien-1-ol) was prepared in 98% yield (30.8 mg) with 94% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a clear liquid. [α] 25 D = 85.6 ( c 1.86, dichloromethane); 1 H NMR (800MHz, CDCl3) δ 7.92 – 7.48 (m, 5H), 7.13 – 6.96 (m, 4H), 6.19 – 6.11 (m, 1H), 4.37 (dd, J = 2.7, 1.0 Hz, 2H), 3.99 (qd, J = 14.1, 1.7 Hz, 2H), 2.75 (s,1H), 2.20 (s, 3H). 13 C NMR (201 MHz, CDCl3) δ 207.2, 138.0, 135.4, 133.9,130.8, 130.5, 129.3, 128.5, 127.9, 127.8, 126.3, 96.9, 94.7, 62.72, 62.71,57.4, 19.8. ESI-HRMS calculated: C 18 H 18 NaO3S + [M+Na] + 337.0869, found: 337.0869. HPLC analysis: 94% ee (IA, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 15.590 min (minor peak), 13.683 min (major peak).

[0157] 6ga ((S)-2-((phenylsulfonyl)methyl)-4-(m-tolyl)buta-2,3-dien-1-ol) was prepared according to the general procedure described above in 96% yield (30.1 mg) with 93% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a clear liquid. [α] 25 D = 90.8 ( c 0.71, dichloromethane); 1H NMR (800MHz, CDCl3) δ 7.99 – 7.49 (m, 5H), 7.17 – 6.84 (m, 4H), 6.01 (p, J = 2.2 Hz,1H), 4.38 (dd, J = 2.7, 1.2 Hz, 2H), 4.09 – 3.95 (m, 2H), 2.57 (s, 1H), 2.30 (s, 3H). 13 C NMR (201 MHz, CDCl3) δ 206.6, 138.4, 138.1, 133.9, 132.3, 129.3, 128.7, 128.6, 128.4, 128.0, 124.4, 97.7, 97.5, 62.6, 57.4, 21.3. ESI-HRMS calculated: C 18 H 18 NaO3S + [M+Na] + 337.0869, found: 337.0869. HPLC analysis: 93% ee (IA, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 20.870 min (minor peak), 13.677 min (major peak).

[0158] 6ha((S)-2-((phenylsulfonyl)methyl)-4-(p-tolyl)buta-2,3-dien-1-ol) was prepared using the general procedure described above in 98% yield (31.0 mg) with 94% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a white solid. [α] 25 D = 82.3 ( c 0.60, dichloromethane); 1 H NMR (400 MHz, CDCl3) δ 8.01 – 7.50 (m, 5H), 7.11 – 6.89 (m, 4H), 6.04 (t, J = 2.4Hz, 1H), 4.37 (d, J = 2.6 Hz, 2H), 4.00 (t, J = 1.9 Hz, 2H), 2.51 (s, 1H), 2.31 (s, 3H). 13C NMR (201 MHz, CDCl3) δ 206.6, 138.4, 138.1, 133.9, 132.3,129.3, 128.7, 128.6, 128.4, 127.9, 124.4, 97.7, 97.5, 62.6, 57.4, 21.3. ESI-HRMS calculated: C 18 H 18 NaO3S + [M+Na] + 337.0869, found: 337.0864. HPLC analysis: 94% ee (AD-H, 15% isopropanol / n-hexane, 1.0 ml / min, UV: 254 nm), t R = 17.583 min (minor peak), 14.920 min (major peak).

[0159] Following the general procedure above, 6ia ((S)-4-(2-methoxyphenyl)-2-((phenylsulfonyl)methyl)buta-2,3-dien-1-ol) was prepared in 85% yield (28.1 mg) with 80% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a clear liquid. [α] 25 D = 79.8 ( c 0.54, dichloromethane); 1 HNMR (400 MHz, CDCl3) δ 7.98 – 7.44 (m, 5H), 7.24 – 6.73 (m, 4H), 6.43 (td, J = 2.6, 1.3 Hz, 1H), 4.36 (d, J = 2.7 Hz, 2H), 3.99 (dd, J = 3.3, 1.8 Hz, 2H), 3.79 (s, 3H), 2.58 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 207.2, 156.2, 138.1,133.9, 129.3, 129.0, 128.6, 128.4, 120.84, 120.80, 110.9, 96.7, 91.7, 62.7,57.6, 55.6. ESI-HRMS calculated: C 18 H 18 NaO4S + [M+Na] +353.0818, found: 353.0828. HPLC analysis: 80% ee (IA, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 30.763 min (minor peak), 16.697 min (major peak).

[0160] 6ja ((S)-4-(3-methoxyphenyl)-2-(phenylsulfonyl)methyl)buta-2,3-dien-1-ol was prepared according to the general procedure described above in 85% yield (28.1 mg) and 93% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a clear liquid. [α] 25 D = 102.1 ( c 1.03, dichloromethane); 1 HNMR (800 MHz, CDCl3) δ 7.99 – 7.35 (m, 5H), 7.17 (t, J = 7.9 Hz, 1H), 6.82 –6.68 (m, 3H), 6.07 (p, J = 2.1 Hz, 1H), 4.37 (d, J = 2.6 Hz, 2H), 4.10 – 3.89(m, 2H), 3.79 (s, 3H), 2.58 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 206.8, 159.9,138.3, 134.0, 133.9, 129.7, 129.4, 128.3, 119.9, 113.6, 112.6, 97.8, 97.5,62.6, 57.4, 55.3. ESI-HRMS calculated: C 18 H 18 NaO4S + [M+Na] + 353.0818, found: 353.0811. HPLC analysis: 93% ee (IA, 15% isopropanol / n-hexane, 1.0 ml / min, UV: 254 nm), t R = 32.133 min (minor peak), 19.497 min (major peak).

[0161] 6ka ((S)-4-(4-methoxyphenyl)-2-(phenylsulfonyl)methyl)buta-2,3-dien-1-ol) was prepared using the general procedure described above in 94% yield (31.0 mg) with 92% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a clear liquid. [α] 25 D = 77.0 ( c 0.47, dichloromethane); 1 HNMR (400 MHz, CDCl3) δ 8.06 – 7.81 (m, 2H), 7.74 – 7.51 (m, 3H), 7.12 – 6.71(m, 4H), 6.05 (td, J = 2.6, 1.3 Hz, 1H), 4.36 (d, J = 2.6 Hz, 2H), 3.99 (t, J = 1.4 Hz, 2H), 3.79 (s, 3H), 2.50 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 206.2, 159.4, 138.2, 133.9, 129.4, 128.5, 128.4, 124.6, 114.2, 97.7, 97.0, 62.7, 57.6, 55.4. Electrospray ionization high-resolution mass spectrometry calculated: C 18 H 18 NaO4S + [M+Na] + 353.0818, found: 353.0812. HPLC analysis: 92% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R =43.337 min (minor peak), 41.603 min (major peak).

[0162] 6la ((S)-4-([1,1'-biphenyl]-4-yl)-2-((phenylsulfonyl)methyl)buta-2,3-dien-1-ol) was prepared according to the general procedure described above in 66% yield (24.8 mg) with 91% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a white solid. MP = 124-126°C; [α] 25 D = 265.7( c 1.41, dichloromethane); 1H NMR (800 MHz, CDCl3) δ 8.04 – 7.29 (m, 13H), 7.19 –7.06 (m, 2H), 6.12 (p, J = 2.2 Hz, 1H), 4.40 (d, J = 2.8 Hz, 2H), 4.04 – 4.00(m, 2H), 2.61 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 206.9, 206.9, 140.68,140.67, 140.5, 138.2, 134.0, 131.5, 131.4, 129.4, 128.9, 128.5, 128.4, 127.7,127.54, 127.50, 127.4, 126.9, 98.0, 97.9, 97.2, 62.6, 57.4, 57.4. ESI-HRMS calculated: C 23 H 20 NaO3S + [M+Na] + 399.1025, found: 399.1031. HPLC analysis: 91% ee (IA, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 28.923 min (minor peak), 23.930 min (major peak).

[0163] 6ma ((S)-4-cyclohexyl-2-((phenylsulfonyl)methyl)buta-2,3-dien-1-ol) was prepared according to the general procedure described above in 91% yield (27.8 mg) with 92% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a white solid. Melting point = 90-92°C; [α] 25 D = 63.4 ( c 1.89, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.97 – 7.53 (m, 5H), 4.98 (dp, J = 6.2, 1.9 Hz,1H), 4.31 – 4.15 (m, 2H), 3.89 (d, J= 1.8 Hz, 2H), 2.55 (s, 1H), 1.80 – 1.41 (m, 6H), 1.28 – 1.00 (m, 3H), 0.97 – 0.71 (m, 2H). 13 C NMR (201 MHz, CDCl3) δ204.4, 138.1, 133.8, 129.2, 129.1, 128.59, 128.56, 128.56, 100.2, 94.4, 63.0,58.1, 36.9, 32.8, 32.7, 25.8, 25.7. ESI-HRMS calculated: C 17 H 22 NaO3S + [M+Na] + 329.1182, found: 329.1177. HPLC analysis: 92% ee (ID, 15%, 1.0 ml / min, UV: 254 nm), t R = 21.697 min (minor peak), 19.053 min (major peak).

[0164] 6ab((S)-2-(((3-Fluorophenyl)sulfonyl)methyl)-4-phenylbuta-2,3-dien-1-ol) was prepared using the general procedure described above in 98% yield (31.2 mg) with 90% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a clear liquid. [α] 25 D = 185.3 ( c 0.64, dichloromethane); 1 HNMR (600 MHz, CDCl3) δ 7.80 – 7.31 (m, 4H), 7.29 – 6.85 (m, 5H), 6.14 (p, J =2.1 Hz, 1H), 4.46 – 4.21 (m, 2H), 4.11 – 3.93 (m, 2H), 2.44 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 206.7, 162.5 (d, J = 252.6 Hz), 140.2 (d, J = 6.6 Hz),132.2, 131.2(d, J= 7.9 Hz), 128.8, 128.0, 127.3, 124.2(d, J = 3.6 Hz), 121.2(d, J = 21.4 Hz), 115.8 (d, J = 24.4 Hz), 97.6(d, J = 21.4 Hz), 62.56, 57.2. 19 F NMR (376 MHz, CDCl3) δ -108.8. Electrospray ionization high-resolution mass spectrometry calculated: C 17 H 15 FNaO3S + [M+Na] + 341.0618, found: 341.0615. HPLC analysis: 90% ee (AD-H, 10% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 37.783 min (minor peak), 23.633 min (major peak).

[0165] Following the general procedure described above, 6ac ((S)-2-(((4-Fluorophenyl)sulfonyl)methyl)-4-phenylbuta-2,3-dien-1-ol) was prepared in 91% yield (28.6 mg) with 93% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a clear liquid. [α] 25 D = 204.8 ( c 0.46, dichloromethane); 1 HNMR (400 MHz, CDCl3) δ 8.16 – 7.78 (m, 2H), 7.38 – 7.04 (m, 7H), 6.12 (s,1H), 4.39 (q, J = 2.6 Hz, 2H), 4.01 (t, J = 1.8 Hz, 2H), 2.57 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 206.62, 166.0 (d, J = 257.0 Hz).134.1(d, J = 3.4 Hz),132.3, 131.3 (d, J= 9.6 Hz), 128.7, 127.9, 127.3, 116.7 (d, J = 22.8 Hz),97.7 (d, J = 52.7 Hz), 62.6, 57.5. 19 F NMR (376 MHz, CDCl3) δ -102.8. Electrospray ionization high-resolution mass spectrometry calculated: C 17 H 15 FNaO3S + [M+Na] + 341.0618, found: 341.0611. HPLC analysis: 93% ee (IA, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 19.967 min (minor peak), 14.417 min (major peak).

[0166] 6ad ((S)-2-(((3-chlorophenyl)sulfonyl)methyl)-4-phenylbuta-2,3-dien-1-ol) was prepared using the general procedure described above in 94% yield (31.4 mg) with 92% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a clear liquid. [α] 25 D = 85.0 ( c 0.30, dichloromethane); 1 HNMR (800 MHz, CDCl3) δ 7.96 – 7.78 (m, 2H), 7.65 – 7.44 (m, 2H), 7.31 – 7.06(m, 5H), 6.16 (p, J = 2.2 Hz, 1H), 4.53 – 4.26 (m, 2H), 4.06 – 3.87 (m, 2H), 2.38 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 206.7, 139.9, 135.7, 134.1, 132.2,130.6, 128.8, 128.5, 127.9, 127.3, 126.5, 97.8, 97.6, 62.6, 57.2. ESI-HRMS calculated: C 17 H 15 ClNaO3S + [M+Na] +357.0323, found: 357.0324. HPLC analysis: 92% ee (IA, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 17.490 min (minor peak), 12.950 min (major peak).

[0167] Compound 6ae ((S)-2-(((4-chlorophenyl)sulfonyl)methyl)-4-phenylbuta-2,3-dien-1-ol) was prepared using the general procedure described above in 87% yield (29.1 mg) and 92% ee. Purification by flash chromatography on silica gel (33% ethyl acetate / petroleum ether) afforded a white solid. MP = 116-118°C. [α] 25 D = 201.6 ( c 0.85, dichloromethane); 1 H NMR (400 MHz, CDCl3) δ 7.89 – 7.45 (m, 4H), 7.37 – 6.97 (m, 5H), 6.12 (td, J = 2.6, 1.3 Hz, 1H), 4.44 – 4.33 (m, 2H), 4.01 (d, J =1.7 Hz, 2H), 2.52 (t, J = 6.3 Hz, 1H). 13 C NMR (201 MHz, CDCl3) δ 206.6, 140.8, 136.6, 132.3, 129.9, 129.7, 128.8, 128.0, 127.3, 97.7, 97.6, 62.5, 57.3. Electrospray ionization high-resolution mass spectrometry calculated: C 17 H 15 ClNaO3S + [M+Na] + 357.0323, found: 357.0331. HPLC analysis: 92% ee (IA, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 33.700 min (minor peak), 26.393 min (major peak).

[0168] 6af ((S)-2-(((2-bromophenyl)sulfonyl)methyl)-4-phenylbuta-2,3-dien-1-ol) was prepared according to the general procedure described above in 45% yield (17.0 mg) with 62% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a clear liquid. [α] 25 D = 60.8 ( c 0.52, dichloromethane); 1 HNMR (800 MHz, CDCl3) δ 8.17 (dd, J = 7.8, 1.7 Hz, 1H), 7.69 (dd, J = 7.9, 1.2Hz, 1H), 7.47 (dtd, J = 45.7, 7.6, 1.5 Hz, 2H), 7.34 – 7.19 (m, 3H), 7.12 –7.01 (m, 2H), 6.18 – 6.05 (m, 1H), 4.56 – 4.22 (m, 4H), 2.42 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 206.5, 137.5, 135.5, 134.9, 132.4, 132.4, 128.7, 128.0,127.8, 127.3, 121.1, 97.7, 97.5, 62.6, 54.6. Electrospray ionization high-resolution mass spectrometry calculated: C 17 H 15 BrNaO3S + [M+Na] + 400.9817, found: 400.9825. HPLC analysis: 62% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 17.280 min (minor peak), 18.740 min (major peak).

[0169] Following the general procedure above, 6ag ((S)-2-(((3-bromophenyl)sulfonyl)methyl)-4-phenylbuta-2,3-dien-1-ol) was prepared in 98% yield (37.0 mg) with 90% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a clear liquid. [α] 25 D = 115.0 ( c0.44, dichloromethane); 1 HNMR (800 MHz, CDCl3) δ 8.07 (t, J = 1.8 Hz, 1H), 7.90 – 7.75 (m, 2H), 7.40(t, J = 7.9 Hz, 1H), 7.32 – 7.17 (m, 3H), 7.17 – 6.96 (m, 2H), 6.16 (q, J =2.2 Hz, 1H), 4.40 (d, J = 2.6 Hz, 2H), 4.13 – 3.93 (m, 2H), 2.34 (s, 1H). 13 CNMR (201 MHz, CDCl3) δ 206.7, 140.1, 137.0, 132.2, 131.3, 130.9, 128.8,128.0, 127.3, 126.9, 123.4, 97.8, 97.6, 62.6, 57.2. ESI-HRMS calculated: C 17 H 15 BrNaO3S + [M+Na] + 400.9817, found: 400.9826. HPLC analysis: 90% ee (IA, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 16.167 min (minor peak), 13.713 min (major peak).

[0170] Following the general procedure above, 6ah ((S)-2-(((4-bromophenyl)sulfonyl)methyl)-4-phenylbuta-2,3-dien-1-ol) was prepared in 84% yield (31.7 mg) with 90% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a clear liquid. [α] 25 D = 193.1 ( c 0.67, dichloromethane); 1 HNMR (800 MHz, CDCl3) δ 7.89 – 7.58 (m, 4H), 7.43 – 6.92 (m, 5H), 6.13 (t, J =2.2 Hz, 1H), 4.39 (dq, J= 6.4, 2.8 Hz, 2H), 4.01 (d, J = 1.8 Hz, 2H), 2.47(t, J = 6.5 Hz, 1H). 13 C NMR (201 MHz, CDCl3) δ 206.6, 137.1, 132.7, 132.2,129.9, 129.4, 128.8, 128.0, 127.3, 97.69, 97.66, 62.5, 57.3. ESI-HRMS calculated: C 17 H 15 BrNaO3S + [M+Na] + 400.9817, found: 400.9807. HPLC analysis: 90%ee (IA, 15% isopropanol / n-hexane, 1.0 ml / min, UV: 254 nm), t R = 19.163 min (minor peak), 16.323 min (major peak).

[0171] Following the general procedure above, 6ai ((S)-4-phenyl-2-((m-toluenesulfonyl)methyl)buta-2,3-dien-1-ol) was prepared in 98% yield (30.8 mg) with 96% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a clear liquid. [α] 25 D = 58.7 ( c 0.38, dichloromethane); 1 H NMR (800MHz, CDCl3) δ 7.73 (dd, J = 6.3, 1.6 Hz, 2H), 7.51 – 7.35 (m, 2H), 7.28 –7.18 (m, 3H), 7.10 – 7.06 (m, 2H), 6.13 (p, J = 2.1 Hz, 1H), 4.39 (dd, J =4.9, 2.6 Hz, 2H), 4.00 (d, J = 1.7 Hz, 2H), 2.41 (s, 3H), 1.73 (s, 1H). 13CNMR (201 MHz, CDCl3) δ 206.6, 139.7, 138.1, 134.8, 132.5, 129.2, 128.7,128.6, 127.8, 127.3, 125.5, 97.9, 97.5, 62.6, 57.4, 21.3. ESI-HRMS calculated: C 18 H 18 NaO3S + [M+Na] + 337.0869, found: 337.0878. HPLC analysis: 96% ee (AD-H, 10% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 27.507 min (minor peak), 21.090 min (major peak).

[0172] Compound 6aj ((S)-4-phenyl-2-(tosylmethyl)buta-2,3-dien-1-ol) was prepared using the general procedure described above in 99% yield (31.1 mg) with 92% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a white solid. MP = 116-118°C. [α] 25 D = 137.3 ( c 1.61, dichloromethane); 1 H NMR (400 MHz, CDCl3) δ 7.85 – 7.28 (m, 4H), 7.28 – 7.01 (m, 5H), 6.11 (dq, J = 2.6, 1.3 Hz, 1H), 4.38 (d, J = 3.3 Hz, 2H), 3.99 (d, J = 1.7Hz, 2H), 2.65 – 2.56 (m, 1H), 2.44 (s, 3H). 13 C NMR (201 MHz, CDCl3) δ 206.6, 145.0, 135.2, 132.5, 130.0, 128.6, 128.4, 127.8, 127.3, 98.0, 97.4, 62.6, 57.5, 21.7. ESI-HRMS calculated: C 18 H 19 O3S + [M+H] +315.1049, found: 315.1046. HPLC analysis: 92% ee (IB, 10% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 18.720 min (minor peak), 19.797 min (major peak).

[0173] Following the general procedure above, 6ak ((S)-2-(((3-methoxyphenyl)sulfonyl)methyl)-4-phenylbuta-2,3-dien-1-ol) was prepared in 82% yield (27.1 mg) with 92% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a clear liquid. [α] 25 D = 87.0 ( c 0.76, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.57 – 7.35 (m, 3H), 7.30 – 7.07 (m, 6H), 6.16 (p, J = 2.1 Hz, 1H), 4.39 (t, J = 2.8 Hz, 2H), 4.01 (d, J = 1.7 Hz, 2H), 3.84 (s, 3H), 2.15 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 206.7, 160.1, 139.3, 132.4,130.4, 128.7, 127.8, 127.3, 120.6, 120.5, 112.7, 97.8, 97.5, 62.6, 57.3,55.8. ESI-HRMS calculated: C 18 H 18 NaO4S + [M+Na] + 353.0818, found: 353.0819 HPLC analysis: 92% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 38.833 min (minor peak), 28.183 min (major peak).

[0174] 6al ((S)-2-(((4-methoxyphenyl)sulfonyl)methyl)-4-phenylbuta-2,3-dien-1-ol) was prepared according to the general procedure described above in 87% yield (28.7 mg) with 91% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a clear liquid. [α] 25 D = 201.6 ( c 1.01, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.91 – 7.75 (m, 2H), 7.37 – 7.04 (m, 5H), 7.01– 6.83 (m, 2H), 6.13 (t, J = 2.2 Hz, 1H), 4.44 – 4.31 (m, 2H), 3.98 (d, J =1.7 Hz, 2H), 3.86 (s, 3H), 2.69 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 206.6, 164.0, 132.6, 130.6, 129.5, 128.7, 127.8 127.3, 114.6, 98.2, 97.3, 62.6, 57.7, 55.7. ESI-HRMS calculated: C 18 H 18 NaO4S + [M+Na] + 353.0818, found: 353.0822. HPLC analysis: 91% ee (IA, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 22.687 min (minor peak), 20.693 min (major peak).

[0175] 6am ((S)-2-(((4-nitrophenyl)sulfonyl)methyl)-4-phenylbuta-2,3-dien-1-ol) was prepared according to the general procedure described above in 91% yield (31.4 mg) with 87% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a white solid. MP = 118-121°C; [α] 25 D = 154.9( c 0.77, dichloromethane); 1H NMR (800 MHz, CDCl3) δ 8.33 – 8.03 (m, 4H), 7.39 – 6.95 (m, 5H), 6.15 (p, J = 2.1 Hz, 1H), 4.41 (t, J = 2.5 Hz, 2H), 4.09 (qd, J =14.3, 1.7 Hz, 2H), 2.36 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 206.7, 150.8, 143.8, 132.0, 129.8, 128.7, 128.2, 127.3, 124.4, 98.0, 97.2, 62.5, 56.9. ESI-HRMS calculated: C 17 H 15 NNaO5S + [M+Na] + 368.0563, found: 368.0568. HPLC analysis: 87% ee (IA, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R =56.103 min (minor peak), 32.913 min (major peak).

[0176] 6an ((S)-4-phenyl-2-((4-(trifluoromethyl)phenyl)sulfonyl)methyl)buta-2,3-dien-1-ol was prepared according to the general procedure described above in 75% yield (27.6 mg) with 90% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a clear liquid. [α] 25 D = 202.9 ( c 0.88, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.89 (dd, J = 224.6, 8.2 Hz, 4H), 7.34 –6.98 (m, 5H), 6.06 (t, J = 2.2 Hz, 1H), 4.50 – 4.32 (m, 2H), 4.15 – 3.97 (m,2H), 2.62 (d, J = 5.5 Hz, 1H). 13C NMR (201 MHz, CDCl3) δ 206.6, 141.7, 135.6(q, J = 33.2 Hz), 132.2, 129.1, 129.0, 128.8, 128.1, 127.3, 126.4 (q, J = 3.7Hz), 123.1 (q, J = 273.0 Hz), 97.7, 97.5, 62.5, 56.9. 19 F NMR (376 MHz, CDCl3)δ -63.2. Electrospray ionization high-resolution mass spectrometry calculated value: C 18 H 16 F3O3S + [M+H] + 369.0767, found: 369.0772. HPLC analysis: 90% ee (AD-H, 10% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 14.333 min (minor peak), 11.920 min (major peak).

[0177] Compound 6ao ((S)-2-(([1,1'-biphenyl]-4-sulfonyl)methyl)-4-phenylbuta-2,3-dien-1-ol) was prepared according to the general procedure described above in 83% yield (31.2 mg) with 92% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a white solid. MP = 84-86°C; [α] 25 D =212.1 ( c 0.33, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 8.04 – 7.66 (m, 4H), 7.63 – 7.40 (m, 5H), 7.23 – 7.03 (m, 5H), 6.11 (p, J = 2.1 Hz, 1H), 4.42 (t, J =3.0 Hz, 2H), 4.05 (t, J = 1.8 Hz, 2H), 2.59 (s, 1H). 13C NMR (201 MHz, CDCl3)δ 206.6, 147.0, 139.0, 136.6, 132.4, 129.2, 128.9, 128.8, 128.7, 127.9,127.8, 127.44, 127.3, 97.9, 97.5, 62.7, 57.5. ESI-HRMS calculated: C 23 H 20 NaO3S + [M+Na] + 399.1025, found: 399.1026. HPLC analysis: 92% ee (IA, 15% isopropanol / n-hexane, 1.0 ml / min, UV: 254 nm), t R = 31.350 min (minor peak), 25.843 min (major peak).

[0178] 6ap ((S)-2-(((3,4-dichlorophenyl)sulfonyl)methyl)-4-phenylbuta-2,3-dien-1-ol) was prepared according to the general procedure described above in 83% yield (30.5 mg) with 90% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a white solid. MP = 102-104°C; [α] 25 D = 190.1 ( c 1.41, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 8.00 (d, J = 2.2 Hz, 1H), 7.74 –7.48 (m, 2H), 7.34 – 6.89 (m, 5H), 6.18 (p, J = 2.1 Hz, 1H), 4.39 (t, J = 2.9Hz, 2H), 4.03 (t, J = 1.6 Hz, 2H), 2.56 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 206.7, 139.1, 137.9, 134.1, 132.1, 131.4, 130.30, 130.29, 128.8, 128.1,127.4, 127.2, 97.9, 97.5, 62.5, 57.0. Electrospray ionization high-resolution mass spectrometry calculated: C 17 H 14Cl2NaO3S + [M+Na] + 390.9933, found: 390.9923. HPLC analysis: 90% ee (AD-H, 10% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 24.807 min (minor peak), 21.470 min (major peak).

[0179] Following the general procedure above, 6aq ((S)-4-phenyl-2-((thiophen-2-ylsulfonyl)methyl)buta-2,3-dien-1-ol) was prepared in 99% yield (30.3 mg) with 90% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a clear liquid. [α] 25 D = 97.7 ( c 1.56, dichloromethane); 1 H NMR (800MHz, CDCl3) δ 7.72 (ddd, J = 12.6, 4.4, 1.4 Hz, 2H), 7.36 – 7.11 (m, 6H), 6.28 – 6.11 (m, 1H), 4.38 (d, J = 2.7 Hz, 2H), 4.19 – 3.93 (m, 2H), 2.39 (s, 2H). 13 C NMR (201 MHz, CDCl3) δ 206.8, 138.8, 134.9, 134.7, 132.5, 128.7,128.1, 127.9, 127.4, 98.1, 97.6, 62.5, 58.8. ESI-HRMS calculated: C 15 H 14 NaO3S2 + [M+Na] + 329.0277, found: 329.0272. HPLC analysis: 90% ee (AD-H, 10% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 32.377 min (minor peak), 29.920 min (major peak).

[0180] 6ar((S)-2-((naphthalen-2-ylsulfonyl)methyl)-4-phenylbuta-2,3-dien-1-ol) was prepared according to the general procedure described above in 97% yield (34.0 mg) with 92% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a white solid. MP = 124-126°C; [α] 25 D = 196.5 ( c 0.78, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 8.52 (d, J = 1.9 Hz, 1H), 8.11 –7.58 (m, 6H), 7.18 – 6.82 (m, 5H), 6.03 (t, J = 2.3 Hz, 1H), 4.42 (dddd, J =15.6, 12.8, 10.4, 2.7 Hz, 2H), 4.10 (d, J = 2.1 Hz, 2H), 2.60 (t, J = 6.2 Hz,1H). 13 C NMR (201 MHz, CDCl3) δ 206.6, 135.5, 135.0, 132.3, 132.2, 130.4,129.7, 129.53, 129.49, 128.5, 128.1, 127.9, 127.7, 127.1, 122.8, 97.9, 97.5,62.6, 57.4. ESI-HRMS calculated: C 21 H 18 NaO3S + [M+Na] + 373.0869, found: 373.0870. HPLC analysis: 92% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 21.437 min (minor peak), 22.890 min (major peak).

[0181] 6as ((S)-2-(((5-(dimethylamino)naphthalen-2-yl)sulfonyl)methyl)-4-phenylbuta-2,3-dien-1-ol) was prepared according to the general procedure described above in 80% yield (31.4 mg) with 75% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a yellow solid. M.P. = 118-120°C; [α] 25 D = 206.1 ( c 1.75, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 8.58 (d, J = 8.5 Hz,1H), 8.43 – 8.22 (m, 2H), 7.54 (dd, J = 8.6, 7.3 Hz, 2H), 7.24 – 6.94 (m,6H), 5.98 (t, J = 2.2 Hz, 1H), 4.37 (dd, J = 4.5, 2.6 Hz, 2H), 4.19 (dd, J =4.6, 1.7 Hz, 2H), 2.84 (s, 6H), 2.69 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 206.5, 152.2, 133.5, 132.5, 131.8, 131.0, 130.4, 129.8, 129.0, 128.6, 127.7,127.3, 123.4, 118.3, 115.4, 97.9, 97.3, 62.7, 56.8, 45.38, 45.37. ESI-HRMS calculated: C 23 H 24 NO3S + [M+H] + 394.1471, found: 394.1461. HPLC analysis: 75% ee (OD-H, 10% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 25.507 min (minor peak), 30.100 min (major peak).

[0182] 6at((S)-2-(((4-(5-methyl-3-phenylisoxazol-4-yl)phenyl)sulfonyl)methyl)-4-phenylbuta-2,3-dien-1-ol) was prepared according to the general procedure described above in 88% yield (40.2 mg) with 90% ee. Purification by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) afforded a clear liquid. [α] 25 D =158.6 ( c 0.72, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.95 – 7.88 (m, 2H), 7.41 – 7.13 (m, 12H), 6.16 – 6.06 (m, 1H), 4.39 (t, J = 2.9 Hz, 2H), 4.10 – 3.97(m, 2H), 2.45 (d, J = 1.2 Hz, 3H). 13 C NMR (201 MHz, CDCl3) δ 206.7, 167.5,161.1, 137.3, 136.7, 132.4, 130.4, 129.9, 128.9, 128.80, 128.77, 128.5,128.3, 128.0, 127.3, 114.3, 97.9, 97.5, 62.68, 62.67, 57.2, 11.9. ESI-HRMS calculated: C 27 H 24 NO4S + [M+H] + 458.1421, found: 458.1413. HPLC analysis: 90% ee (IA, 15% isopropanol / n-hexane, 1.0 ml / min, UV: 254 nm), t R = 39.440 min (minor peak), 22.233 min (major peak).

[0183] Derivatization and application of reaction products

[0184] The axially chiral allenol products 4ba-4na, 4aa-4az, 8aa-8ah, 4aac, 6ba-6ma, and 6aa-6at have been used in the synthesis of chiral allenol ethers, chiral allenamides, chiral oxygen heterocycles, chiral allenaldehydes, and chiral allenesters. This method has also been applied to the one-pot synthesis of chiral vinylcyclopropane alcohol derivatives. Furthermore, optical characterization of the axially chiral fluorescent compounds 5aa-5al revealed their excellent fluorescent activity, suggesting their potential as novel chiral fluorescent probes for applications in medicine and materials.

[0185] Take 4aa, 8ah, 4aac, 6aa, 6at and 5ai as examples.

[0186] like Figure 9 Under argon, a Shrek tube was charged with chiral allenol 4aa (0.1 mmol, 1.0 equiv), NaH (0.4 mmol, 4.0 equiv), and tetrahydrofuran (2 mL) and cooled to 0°C. After stirring at room temperature for 15 minutes, benzyl bromide (0.15 mmol, 1.5 equiv) dissolved in tetrahydrofuran (1 mL) was added to the reaction system. The reaction mixture was stirred at room temperature until the disappearance of substrate 4aa (monitored by thin-layer chromatography). The reaction was quenched with 1 mL of saturated sodium chloride solution at 0°C and extracted with ethyl acetate. The organic layers were combined, dried, and concentrated. The crude product was purified by flash silica gel column chromatography (50% ethyl acetate / petroleum ether) to afford product 9 (22.3 mg, 65% yield, 95% ee) as a colorless oil.

[0187] Product data 9: (R)-1-(2-(Benzyloxy)methyl)-4-phenylbuta-2,3-dien-1-yl)pyridin-2(1H)-one[α] 25 D = 52.0 ( c 0.30, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.41 – 7.14 (m,12H), 6.51 (dd, J = 9.2, 1.2 Hz, 1H), 6.28 (t, J = 2.6 Hz, 1H), 6.05 (td, J =6.6, 1.4 Hz, 1H), 4.80 – 4.53 (m, 4H), 4.21 (t, J = 1.9 Hz, 2H). 13C NMR (201 MHz, CDCl3) δ 203.4, 162.4, 139.5, 137.8, 133.4, 131.6, 128.68, 128.67,128.5, 128.0, 127.8, 127.5, 127.1, 121.0, 105.8, 103.1, 98.3, 72.2, 69.3,48.2. ESI-HRMS calculated: C 23 H 22 NO2 + [M+H] + 344.1645, found: 344.1642. HPLC analysis 95% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 36.213 min (minor peak), 29.517 min (major peak).

[0188] like Figure 10 Under argon atmosphere, p-toluene isocyanate (0.12 mmol, 1.2 eq) and triethylamine (0.20 mmol, 2.0 eq) were added dropwise to a solution of chiral allenol 4aa (25.3 mg, 0.10 mmol, 1.0 eq) in 1 mL of dichloromethane at room temperature. The reaction was stirred overnight, and after monitoring by thin-layer chromatography, the solvent was removed under vacuum. The residue was purified on a silica gel column (60% ethyl acetate / petroleum ether) to afford the liquid product 10 (37.4 mg, 97% yield, 94% ee).

[0189] Product data 10: (R)-2-((2-oxopyridin-1(2H)-yl)methyl)-4-phenylbuta-2,3-dien-1-yl p-tolylcarbamate [α] 25 D = 51.4 ( c 1.44, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ7.32 – 7.04 (m, 11H), 6.52 (dd, J = 9.4, 1.4 Hz, 1H), 6.33 (p, J = 2.6 Hz,1H), 6.07 (td, J = 6.7, 1.4 Hz, 1H), 4.86 – 4.66 (m, 4H), 2.33 (s, 1H), 2.28 (s, 3H). 13C NMR (201 MHz, CDCl3) δ 203.9, 162.5, 139.8, 137.4, 132.9, 129.5,128.7, 127.7, 127.2, 120.9, 106.3, 102.5, 99.3, 63.2, 47.8, 20.8. ESI-HRMS calculated: C 24 H 23 N2O3 + [M+H] + 387.1703, found: 387.1711. HPLC analysis: 94% ee (OD-H, 10% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 24.617 min (minor peak), 31.253 min (major peak).

[0190] like Figure 11 Under an argon atmosphere, silver p-toluenesulfonate (5 mol %) and triphenylphosphine gold chloride (5 mol %) were added to a dry Shrek tube containing 1 mL of chloroform. After stirring at room temperature for 30 minutes, the resulting mixture was stirred at -30°C for another 10 minutes, and then 4aa (25.3 mg, 0.10 mmol, 1.0 eq) was dissolved in 1 mL of chloroform and added to the reaction system. After the resulting mixture was stirred at -30°C for 12 hours, the solvent was removed under vacuum. The residue was purified on a silica gel column (60% ethyl acetate / petroleum ether) to obtain the product 11 as a white solid (24.8 mg, 98% yield, 94% ee).

[0191] Product data 11: (S)-1-((5-phenyl-2,5-dihydrofuran-3-yl)methyl)pyridin-2(1H)-one melting point = 120–122°C; [α] 25 D = -46.6 ( c 2.18, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.35 –7.26 (m, 7H), 6.59 (dd, J = 9.2, 1.3 Hz, 1H), 6.19 (td, J = 6.7, 1.4 Hz, 1H),5.80 (tt, J = 3.9, 1.9 Hz, 1H), 5.70 (q, J= 1.9 Hz, 1H), 4.83 – 4.69 (m,4H). 13 C NMR (201 MHz, CDCl3) δ 162.3, 141.4, 139.7, 136.9, 136.6, 128.6, 128.0, 127.6, 126.3, 121.3, 106.5, 88.1, 75.7, 45.5. ESI-HRMS calculated: C 16 H 16 NO2 + [M+H] + 254.1176, found: 254.1167. HPLC analysis: 94% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 48.257 min (minor peak), 32.993 min (major peak).

[0192] like Figure 12 , in a dry Shrek tube, N Iodosuccinimide (NIS, 2.0 equiv) was dissolved in 1 mL of dichloromethane and added dropwise at -15°C to a solution of 4aa (25.3 mg, 0.10 mmol, 1.0 equiv) in 1 mL of dichloromethane. The reaction was stirred at 0°C until the starting material was consumed, as determined by thin-layer chromatography (TLC). The reaction mixture was diluted with ethyl acetate and washed with 1 mL of saturated sodium thiosulfate solution. The aqueous layers were combined and extracted with 5 mL of ethyl acetate. All organic layers were combined, dried over anhydrous sodium sulfate, and the solvent removed under vacuum. The residue was purified on a silica gel column (50% ethyl acetate / petroleum ether) to yield the viscous liquid product 12 (32.2 mg, 85% yield, 91% ee).

[0193] Product data 12: (R)-1-((4-iodo-5-phenyl-2,5-dihydrofuran-3-yl)methyl)pyridin-2(1H)-one[α] 25 D = -56.1 ( c 0.99, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 7.39 – 7.26 (m,7H), 6.59 (d, J = 9.0 Hz, 1H), 6.20 (t, J = 6.6 Hz, 1H), 5.62 (t, J= 4.0 Hz,1H), 4.92 – 4.64 (m, 4H). 13 C NMR (201 MHz, CDCl3) δ 140.5, 139.9, 139.2, 136.9, 128.8, 128.6, 127.6, 106.8, 96.2, 93.2, 76.7, 47.4. ESI-HRMS calculated: C 16 H 15 INO2 + [M+H] + 380.0142 Found: 380.0140. HPLC analysis: 91% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 17.540 min (minor peak), 14.753 min (major peak).

[0194] like Figure 13 In a dry reaction flask, chiral allenol 8ah (45.4 mg, 0.10 mmol, 1.0 eq) was dissolved in 1 mL of acetonitrile. Dess-Martin periodinane (1.2 eq) was added in one portion at 0°C. After confirming the reaction was complete by thin-layer chromatography, the solvent was removed under vacuum, and the residue was purified by flash silica gel column chromatography (33% ethyl acetate / petroleum ether) to afford the viscous liquid product 13 (36.2 mg, 80% yield, 67% ee).

[0195] Product data 13: (R)-2-(2,2-bis(phenylsulfonyl)ethyl)-4-phenylbuta-2,3-dienal[α] 25 D = -3.2 ( c 1.01, dichloromethane); 1 H NMR (600 MHz, Chloroform- d ) δ 9.54 (s, 1H), 7.96(d, J = 7.9 Hz, 2H), 7.87 (d, J = 7.8 Hz, 2H), 7.73 – 7.20 (m, 16H), 6.88 (d, J = 2.8 Hz, 1H), 4.99 (t, J = 6.2 Hz, 1H), 3.18 (qdd, J = 16.7, 6.3, 2.8 Hz,2H).13 C NMR (201 MHz, CDCl3) δ 203.1, 134.2, 128.68, 128.66, 128.65, 128.49,128.47, 127.82, 127.80, 127.4, 127.1, 126.9, 126.8, 103.4, 94.8, 65.4, 63.6,57.6, 38.1, 18.1. ESI-HRMS calculated: C 24 H 20 NaO5S2 + [M+Na] + 475.0644, found: 475.0651. HPLC analysis: 67% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 70.920 min (minor peak), 51.023 min (major peak).

[0196] like Figure 14 Under a nitrogen atmosphere, magnesium turnings (2 mmol) and methanol (4 mL) were added to a dry Shrek tube. A solution of 8ah (45.4 mg, 0.10 mmol) in tetrahydrofuran (1 mL) was added with stirring at 0°C, followed by warming to room temperature. After stirring for 3 hours, the reaction was confirmed complete by thin-layer chromatography. Ether (5 mL) was added to dilute the reaction, and the resulting mixture was filtered through a short silica gel column and eluted with ether (10 mL x 3). The solvent was removed under vacuum, and the residue was purified by flash silica gel column chromatography (16% ethyl acetate / petroleum ether) to obtain the liquid product 14 (17.1 mg, 98% yield, 90% ee).

[0197] Product data: 14: (R)-2-ethyl-4-phenylbuta-2,3-dien-1-ol [α] 25 D = -8.5 ( c 0.82, dichloromethane); 1 H NMR (600 MHz, CDCl3) δ 7.30 (d, J = 4.3 Hz, 5H), 6.44 – 6.33 (m,1H), 4.24 – 4.12 (m, 2H), 2.16 (td, J = 7.8, 3.3 Hz, 2H), 2.01 (s, 1H), 1.10(t, J = 7.4 Hz, 3H). 13C NMR (201 MHz, CDCl3) δ 200.2, 134.9, 128.7, 127.1, 126.7, 126.6, 111.8, 99.0, 631, 22.7, 12.2. ESI-HRMS calculated: C 12 H 14 NaO + [M+Na] + 197.0937, found: 197.0927. HPLC analysis: 90% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 4.513 min (minor peak), 4.777 min (major peak).

[0198] like Figure 15 Compound 4aac (36.9 mg, 0.10 mmol, 1.0 eq), 4-dimethylaminopyridine (DMAP, 0.2 eq), and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI, 1.2 eq) were dissolved in 3 mL of anhydrous dichloromethane at room temperature. (S)-(+)-ibuprofen (1.0 eq) was added, and the reaction was stirred overnight. After TLC monitoring indicated the reaction was complete, the solvent was removed under vacuum. The residue was purified by flash silica gel column chromatography (67% ethyl acetate / petroleum ether) to obtain the liquid product 15a (54.6 mg, 98% yield, 95% ee).

[0199] Product Data 15a: (R)-2-((5-cyano-2-methyl-6-oxo-[3,4-bipyridyl]-1(6H)-yl)methyl)-4-phenylbuta-2,3-dien-1-yl (R)-2-(4-isobutylphenyl)propionate [α] 25 D = 284.7 ( c 2.23, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 8.53 (d, J = 5.5 Hz, 2H), 7.47 (s, 1H),7.33 – 7.24 (m, 3H), 7.24 – 7.19 (m, 2H), 7.11 – 7.03 (m, 4H), 6.63 (s, 2H),6.24 (tt, J = 3.8, 2.2 Hz, 1H), 4.98 (s, 1H), 4.83 (ddd, J= 162.8, 12.6, 2.3Hz, 2H), 4.47 (s, 1H), 3.75 (q, J = 7.2 Hz, 1H), 2.38 (d, J = 7.2 Hz, 2H), 2.00 (s, 3H), 1.78 – 1.71 (m, 1H), 1.50 (d, J = 7.2 Hz, 3H), 0.84 (d, J = 6.7Hz, 6H). 13 C NMR (201 MHz, CDCl3) δ 201.9, 174.3, 159.3, 150.7, 150.2, 146.6,144.8, 140.8, 137.4, 132.2, 129.4, 128.9, 128.1, 127.3, 127.1, 124.1, 117.8,115.3, 102.1, 101.4, 100.9, 62.7, 45.1, 44.9, 43.9, 30.1, 22.3, 22.3, 18.2,18.0. ESI-HRMS calculated: C 36 H 35 N3NaO3 + [M+Na] + 580.2571, found: 580.2586. HPLC analysis: 95% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 23.960 min (minor peak), 18.997 min (major peak).

[0200] like Figure 16 Compound 4aac (36.9 mg, 0.10 mmol, 1.0 eq), 4-dimethylaminopyridine (DMAP, 0.2 eq), and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI, 1.2 eq) were dissolved in 3 mL of anhydrous dichloromethane at room temperature. (S)-naproxen (1.0 eq) was added, and the reaction was stirred overnight. After TLC monitoring indicated the reaction was complete, the solvent was removed under vacuum. The residue was purified by flash silica gel column chromatography (67% ethyl acetate / petroleum ether) to afford 15b as a white solid (55.3 mg, 93% yield, 96% ee).

[0201] Product data 15b: (R)-2-((5-Cyano-2-methyl-6-oxo-[3,4-bipyridinyl]-1(6H)-yl)methyl)-4-phenylbuta-2,3-dien-1-yl (R)-2-(6-methoxynaphthalen-2-yl)propanoate m.p. = 68–70°C; [α] 25 D =308.9 ( c 2.23, dichloromethane); 1 H NMR (800 MHz, CDCl3) δ 8.42 (d, J = 5.1 Hz, 2H),7.63 – 7.43 (m, 3H), 7.41 – 7.27 (m, 2H), 7.14 (dd, J = 5.2, 1.9 Hz, 3H),7.09 – 6.81 (m, 4H), 6.43 (d, J = 4.7 Hz, 2H), 6.06 (t, J = 2.9 Hz, 1H), 4.89(dd, J = 12.6, 1.9 Hz, 1H), 4.82 (s, 1H), 4.60 (dd, J = 12.5, 2.4 Hz, 1H), 4.34 (s, 1H), 3.84 – 3.82 (m, 1H), 3.81 (s, 3H), 1.60 (s, 3H), 1.51 (d, J =7.2 Hz, 3H). 13 C NMR (201 MHz, CDCl3) δ 202.0, 174.2, 159.3, 157.8, 150.7,150.1, 146.6, 144.6, 135.3, 133.8, 132.1, 129.2, 128.88, 128.86, 128.0,127.3, 127.0, 126.2, 124.01, 123.99, 119.3, 117.7, 115.4, 105.5, 102.0,101.2, 100.8, 62.8, 55.4, 45.4, 43.9, 18.1, 17.7. Electrospray ionization high-resolution mass spectrometry calculated value: C 38 H 34 N3O4 + [M+H] +596.2544, found: 596.2534. HPLC analysis: 96% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 69.367 min (minor peak), 63.890 min (major peak).

[0202] Palladium-catalyzed one-pot synthesis of chiral vinylcyclopropane alcohol derivatives: Figure 17 Under an argon atmosphere, allenyl dimethylene cyclic carbonate compound 1a (0.15 mmol), bis(benzenesulfonic acid) methane 7h (0.10 mmol), palladium catalyst (Pd2(dba)3) (5 mol%, 0.005 mmol) and ligand (L2: N,N'-[(1R,2R)-1,2-bis(2-methoxy)phenyl-1,2-ethanediyl]bis[2-diphenylphosphinobenzamide] (11 mol%, 0.011 mmol), respectively) were weighed into a Shrek tube. 1 mL of dichloromethane was added, and the reaction was stirred continuously at room temperature. After completion of the reaction was monitored by thin-layer chromatography, the solvent was removed by concentration under reduced pressure. Under an argon atmosphere at 80°C, iodobenzene (1.2 equiv), potassium carbonate (4 equiv), tetrakis(triphenylphosphine)palladium (5 mol%), and 1 mL of tetrahydrofuran were added. After stirring for 12 h, the solvent was removed under reduced pressure and the residue was purified by flash silica gel column chromatography (30% ethyl acetate / petroleum ether) to give the product 16 as a white solid (42.4 mg, 80% yield, 90% ee).

[0203] Product data 16: (1-(1,2-Diphenylvinyl)-2,2-bis(phenylsulfonyl)cyclopropyl)methanol Melting point = 90–92°C; [α] 25 D = -159.9 ( c 1.20, dichloromethane); 1 H NMR (600 MHz, CDCl3) δ 8.12 –8.02 (m, 2H), 7.69 – 7.35 (m, 8H), 7.22 – 7.04 (m, 8H), 6.66 (dd, J = 7.8,1.8 Hz, 2H), 5.15 (d, J = 1.9 Hz, 1H), 4.29 (d, J = 12.8 Hz, 1H), 4.25 – 4.16(m, 2H), 3.71 (d, J = 18.6 Hz, 1H), 1.80 – 1.60 (m, 2H).13 C NMR (201 MHz,CDCl3) δ 140.0, 139.5, 137.2, 135.8, 134.6, 134.0, 133.68, 133.65, 131.1,130.8, 128.9, 128.3, 128.23, 128.19, 128.0, 127.83, 127.77, 95.4, 61.2, 59.1,40.6. ESI-HRMS calculated: C 30 H 26 NaO5S2 + [M+Na] + 553.1114, found: 553.1108. HPLC analysis: 90% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 35.780 min (minor peak), 29.173 min (major peak).

[0204] like Figure 18 To a solution of 6aa (30.0 mg, 0.10 mmol) in dichloromethane (1 mL) at 0°C was added Dess-Martin periodinane (63.6 mg, 0.15 mmol). The reaction mixture was stirred at 0°C. After completion of the reaction as confirmed by thin-layer chromatography, the solvent was removed under vacuum. The product was purified by flash silica gel column chromatography (15% ethyl acetate / petroleum ether) to afford liquid product 17 (82% yield, 24.4 mg).

[0205] Product data 17: 4-phenyl-2-((phenylsulfonyl)methylene)but-3-enal 1 H NMR (800 MHz, CDCl3)δ 9.24 (s, 1H), 8.09 (s, 1H), 7.84 – 7.20 (m, 10H), 6.78 (s, 1H), 6.55 (s, 1H). 13 C NMR (201 MHz, CDCl3) δ 189.1, 141.1, 140.98, 140.90, 138.3, 133.6,133.4, 132.7, 130.6, 129.9, 129.0, 128.9, 128.7. ESI-HRMS calculated: C 17 H 15 O3S + [M+H]+ 299.0736, measured value: 299.0726.

[0206] like Figure 19 , in a dry Shrek tube, N Iodosuccinimide (NIS, 1.2 equiv) was dissolved in 1 mL of dichloromethane and added dropwise at -15°C to a solution of 6aa (30.0 mg, 0.10 mmol, 1.0 equiv) in 1 mL of dichloromethane. The reaction was stirred at 0°C until the starting material was consumed, as determined by thin-layer chromatography (TLC). The reaction mixture was diluted with ethyl acetate and washed with 1 mL of saturated sodium thiosulfate solution. The aqueous layers were combined and extracted with 5 mL of ethyl acetate. All organic layers were combined, dried over anhydrous sodium sulfate, and the solvent removed under vacuum. The residue was purified on a silica gel column (25% ethyl acetate / petroleum ether) to yield the viscous liquid product 18 (41.3 mg, 97% yield, 96% ee).

[0207] Product data 18 (R)-3-iodo-2-phenyl-4-((phenylsulfonyl)methyl)-2,5-dihydrofuran [α] 25 D = -49.6 ( c 2.29, dichloromethane); 1 H NMR (600 MHz, CDCl3) δ 8.08 – 7.45 (m, 5H), 7.39 –7.30 (m, 3H), 7.20 – 7.04 (m, 2H), 5.60 – 5.42 (m, 1H), 4.99 (ddd, J = 120.8,12.8, 4.9 Hz, 2H), 4.22 – 3.81 (m, 2H). 13 C NMR (201 MHz, CDCl3) δ 139.0, 137.6, 134.3, 133.1, 129.5, 128.8, 128.7, 128.5, 127.5, 102.2, 93.3, 57.8. Electrospray ionization high-resolution mass spectrometry calculated: C 17 H 16 IO3S + [M+H] + 426.9859 Found: 426.9863. HPLC analysis: 96% ee (AD-H, 15% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 16.020 min (minor peak), 16.797 min (major peak).

[0208] like Figure 20 Compound 6at (45.7 mg, 0.1 mmol), 4-dimethylaminopyridine (2.4 mg, 0.02 mmol), and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (22.9 mg, 0.12 mmol) were dissolved in 2 ml of anhydrous dichloromethane at room temperature. Isoxepac (26.8 mg, 0.1 mmol) was added, and the reaction was stirred overnight. After TLC monitoring indicated the reaction was complete, the solvent was removed under vacuum. The residue was purified by flash silica gel column chromatography (66% ethyl acetate / petroleum ether) to obtain the liquid product 19 (97% yield, 69.9 mg, 88% ee).

[0209] Product Data 19: (S)-2-(((4-(5-methyl-3-phenylisoxazol-4-yl)phenyl)sulfonyl)methyl)-4-phenylbuta-2,3-dien-1-yl-2-(11-oxo-6,11-dihydrodibenzo[b,e]oxepan-2-yl)acetate [α] 25 D = 51.2 ( c 2.79, dichloromethane); 1 H NMR (600 MHz, CDCl3) δ 8.06 (d, J = 2.4Hz, 1H), 7.93 – 7.83 (m, 3H), 7.50 (dt, J = 58.5, 7.6 Hz, 2H), 7.31 (td, J =21.2, 19.9, 8.6 Hz, 9H), 7.24 – 7.13 (m, 4H), 7.08 (d, J = 7.5 Hz, 2H), 6.91(dd, J = 8.4, 2.1 Hz, 1H), 6.07 (s, 1H), 5.13 (s, 2H), 4.83 (qd, J = 12.8,2.4 Hz, 2H), 3.91 (s, 2H), 3.62 (s, 2H), 2.42 (d, J = 1.9 Hz, 3H). 13C NMR(201 MHz, CDCl3) δ 208.0, 190.7, 170.8, 167.5, 161.1, 160.5, 140.4, 137.2,136.6, 136.4, 135.6, 132.9, 132.5, 131.8, 130.4, 129.8, 129.5, 129.3, 128.9,128.79, 128.75, 128.5, 128.3, 128.1, 127.9, 127.43, 127.38, 125.1, 121.1,114.3, 98.2, 94.5, 73.6, 63.5, 57.3, 40.1, 11.82. Electrospray ionization high-resolution mass spectrometry calculated: C 44 H 36 NO7S + [M+H] + 722.2207, found: 722.2207. HPLC analysis: 88% ee (IA, 20% isopropanol / n-hexane, 1.0 mL / min, UV: 254 nm), t R = 124.517 min (minor peak), 91.803 min (major peak).

[0210] like Figure 21 Compound 6at (45.7 mg, 0.1 mmol), 4-dimethylaminopyridine (2.4 mg, 0.02 mmol), and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (22.9 mg, 0.12 mmol) were dissolved in 2 ml of anhydrous dichloromethane at room temperature. Febuxostat (31.6 mg, 0.1 mmol) was added, and the reaction was stirred overnight. After thin-layer chromatography monitoring showed that the reaction was complete, the solvent was removed under vacuum. The residue was purified by flash silica gel column chromatography (66% ethyl acetate / petroleum ether) to obtain the liquid product 20 (95% yield, 71.6 mg, 91% ee).

[0211] Product Data 20: (S)-2-(((4-(5-methyl-3-phenylisoxazol-4-yl)phenyl)sulfonyl)methyl)-4-phenylbuta-2,3-dien-1-yl-2-(3-cyano-4-isobutoxyphenyl)-4-methylthiazole-5-carboxylate [α] 25 D =59.5 ( c 3.17, dichloromethane); 1H NMR (600 MHz, CDCl3) δ 8.15 – 7.88 (m, 4H), 7.36(q, J = 7.3, 6.6 Hz, 5H), 7.26 (ddt, J = 22.7, 15.3, 7.4 Hz, 4H), 7.08 (dd, J = 95.9, 8.1 Hz, 3H), 6.16 (s, 1H), 5.12 – 4.94 (m, 2H), 4.03 (d, J = 7.7 Hz,2H), 3.90 (d, J = 6.4 Hz, 2H), 2.69 (d, J = 2.6 Hz, 3H), 2.45 (d, J = 2.5 Hz,3H), 2.20 (dt, J = 13.4, 6.7 Hz, 1H), 1.09 (d, J = 6.6 Hz, 6H). 13 C NMR (201MHz, CDCl3) δ 208.3, 167.6, 167.5, 162.6, 161.9, 161.3, 161.1, 137.2, 136.7,132.3, 132.1, 131.8, 130.4, 129.8, 128.9, 128.8, 128.8, 128.5, 128.3, 128.3,127.5, 125.8, 120.9, 115.4, 114.3, 112.7, 102.9, 98.5, 94.5, 75.7, 63.9,57.4, 28.2, 19.1, 17.5, 11.9. Calculated by electrospray ionization high-resolution mass spectrometry: C 44 H 39 N2O6S2 + [M+H] + 755.2244, found: 755.2254. HPLC analysis: 91% ee (IA, 20% isopropanol / n-hexane, 1.0 ml / min, UV: 254 nm), t R = 100.820 min (minor peak), 82.157 min (major peak).

[0212] Taking 5ai as an example, the optical properties test of the axial chiral fluorescent compound 5ai

[0213] Fluorescence spectra of the compounds were measured using a multifunctional microplate reader (Varioskan LUX, Thermo Fisher Scientific, USA). The specific steps were as follows: the target compound was dissolved in different solvents to prepare a solution of appropriate concentration. The solution was then transferred to a 384-well plate (either a clear or black bottom plate, depending on the experimental requirements). Excitation and emission wavelength parameters were set using the instrument software, and fluorescence signals were collected at room temperature. At least three replicates were performed for each sample to ensure data reproducibility and reliability.

[0214] The emission spectra of compound 5ai (5 μM) in different solvents (ethanol, toluene, acetonitrile, N,N-dimethylformamide, acetone, ethyl acetate, dimethyl sulfoxide, dichloroethane, 1,4-dioxane) were measured to evaluate its ubiquitous solvation effect ( Figure 22 ). 5ai (5 μM) was dissolved in different polar solvents (ethanol, toluene, acetonitrile, N,N-dimethylformamide, acetone, ethyl acetate, dimethyl sulfoxide, dichloroethane, 1,4-dioxane), and its emission spectrum was observed at the optimal excitation wavelength. The experiment found that the fluorescence of 5ai was significantly enhanced in polar solvents, which reveals the sensitivity of this compound to environmental changes ( Figure 22 ).

[0215] The present invention evaluated the excitation and emission wavelengths of compound 5ai and found significant differences in different solvents: the emission wavelength red-shifted from 562 nm to 624 nm, a shift of 62 nm, indicating the presence of typical intramolecular charge transfer (ICT) in this reaction. Furthermore, compound 5ai exhibited a large Stokes shift (100-163 nm), which helps reduce self-absorption caused by backscattering (Table 1). In summary, compound 5ai exhibits excellent optical properties.

[0216] Table 1 Spectral characteristics of compound 5ai (excitation wavelength, emission wavelength and Stokes shift)

[0217]

[0218] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. An allenyl dimethylene cyclic carbonate compound, characterized in that: The general structural formula of the compound is shown in I: In formula I, R is selected from Ph, 3-FC6H4, 4-FC6H4, 3-ClC6H4, 4-ClC6H4, 2-MeC6H4, 3-MeC6H4, 4-MeC6H4, 2-MeOC6H4, 3-MeOC6H4, 4-MeOC6H4, 4-PhC6H4, cyclohexyl, 2-nap.

2. The method for preparing the allenyl dimethylene cyclic carbonate compound according to claim 1, wherein: The method comprises the following steps: Under an argon atmosphere, tetrakis(triphenylphosphine)palladium and zinc bromide were dissolved in tetrahydrofuran, and then a Grignard reagent solution was added to react to obtain a crude product of 5-ethynyl-2,2-dimethyl-1,3-dioxane-5-acetate; The crude product of 5-ethynyl-2,2-dimethyl-1,3-dioxane-5-acetate was dissolved in methanol, and concentrated sulfuric acid was added dropwise to react to obtain the product of allenedimethylene glycol; The allenyl dimethylene glycol product is dissolved in dichloromethane, and triethylamine is added dropwise to react; triphosgene is dissolved in dichloromethane and then added dropwise to the above reaction system to react, and after the reaction is completed, the allenyl dimethylene carbonate product is separated and purified to obtain the allenyl dimethylene cyclic carbonate compound.

3. The method for preparing the allenyl dimethylene cyclic carbonate compound according to claim 2, wherein: The Grignard reagent is R-Mg-X, wherein R is Ph, 3-FC6H4, 4-FC6H4, 3-ClC6H4, 4-ClC6H4, 2-MeC6H4, 3-MeC6H4, 4-MeC6H4, 2-MeOC6H4, 3-MeOC6H4, 4-MeOC6H4, 4-PhC6H4, cyclohexyl, 2-nap, and X is Br, Cl, or I.

4. Use of the allenyl dimethylene cyclic carbonate compound according to claim 1 as an intermediate of a trisubstituted axial chiral allenol derivative.

5. A method for preparing a trisubstituted axial chiral allenol derivative, characterized in that: The method comprises the following steps: Under an argon atmosphere, an allenyl dimethylene cyclic carbonate compound represented by general formula I, a nucleophilic reagent, a palladium catalyst, a chiral ligand, and an organic solvent are mixed for reaction. After the reaction is completed by monitoring by thin layer chromatography, the resulting axially chiral allene product is purified by flash silica gel column chromatography to obtain a trisubstituted axially chiral allenol derivative. The general structural formula of the trisubstituted axially chiral allenol derivative is shown in II: In formula II, R is selected from Ph, 3-FC6H4, 4-FC6H4, 3-ClC6H4, 4-ClC6H4, 2-MeC6H4, 3-MeC6H4, 4-MeC6H4, 2-MeOC6H4, 3-MeOC6H4, 4-MeOC6H4, 4-PhC6H4, cyclohexyl, 2-nap; Nu is selected from 2-pyridone, other nitrogen-containing heterocycles, secondary amines, bisbenzenesulfonic acid methane, and sodium arylsulfinate; The nucleophilic reagent is 2-pyridone, other nitrogen-containing heterocyclic substrates, secondary amine substrates, bisbenzenesulfonic acid methane, and sodium arylsulfinate; other nitrogen-containing heterocyclics are 2-hydroxypyrazine, 4-hydroxypyrimidine, 3-methyluracil, 1-hydroxyisoquinoline, 4,5-dihydro-4-oxofurano[3,2]pyridine, 4-hydroxythieno[3,2-C]pyridine, 2-hydroxyquinoxaline, isatin, 2-benzoxazolinone, and 2-hydroxybenzothiazole; the secondary amine is N -Benzylcyclohexylamine, ( S )-(-)- N -methyl-1-phenylethylamine, N -allylbenzylamine, N -Methylbenzylamine, dibenzylamine, morpholine, benzyl-1-piperazine carbonate.

6. The method for preparing a trisubstituted axial chiral allenol derivative according to claim 5, characterized in that: The chiral ligands are (1R,2R)-(+)-1,2-diaminocyclohexane-N,N'-bis(2-phenylphosphino-1-naphthoyl), N,N'-[(1R,2R)-1,2-diphenyl-1,2-ethanediyl]bis[2-diphenylphosphinobenzamide], and N,N'-[(1R,2R)-1,2-bis(2-methoxy)phenyl-1,2-ethanediyl]bis[2-diphenylphosphinobenzamide].

7. The method for preparing a trisubstituted axial chiral allenol derivative according to claim 5, wherein: The molar ratio of the allenyl dimethylene cyclic carbonate compound represented by the general formula I, the nucleophilic reagent, the palladium catalyst, and the chiral ligand is 1:(0.66~2.5):(0.033~0.05):(0.073~0.11).

8. A trisubstituted axial chiral allenol derivative, characterized in that the structural formula As shown below: 。 9. Use of the trisubstituted axial chiral allenol derivative according to claim 8 as a fluorescent compound.

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