High-optical activity o-hydroxyl dihydronaphthalene formate compound and preparation method thereof

Abstract

The invention provides a high-optical-rotation o-hydroxyl dihydronaphthalene formate compound capable of being used as an optical-rotation material monomer and a preparation method of the high-optical-rotation o-hydroxyl dihydronaphthalene formate compound. The o-hydroxyl dihydronaphthalene formate compound is prepared by catalyzing triaryl divinyl ketone to perform asymmetric reaction through a chiral pyridine bisoxazoline rare earth complex. Reaction raw materials are simple and easy to obtain; the product has good stereoselectivity, the yield is up to 95%, and the er value is 98: 2. The synthesized compound can be used as an optical rotation material monomer for preparing an optical rotation material, and has an important prospect in the development of new drugs.

Description

Technical Field

[0001] The present invention belongs to the technical fields of organic synthesis and organic materials, and particularly relates to a class of highly optically active o - hydroxydihydronaphthoate compounds that can be used as monomers of optically active materials and a preparation method thereof. Background Art

[0002] Dihydronaphthoate compounds are not only a key skeletal structure of a class of pesticides (Lindner, W.; Becker, B.; Steffens, R.; Wachendorff - Neumann, U.; Brandes, W.; Dutzmann, S.; Stendel, W. Preparation of substituted 1,4 - naphthoquinones as pesticides. DE3801743 A1 1989 - 01 - 19), and they have good insecticidal effects on the main pests of cotton and corn, as well as the two - spotted spider mite, one of the pests on vegetables, flowers and fruit trees; they also have good bactericidal effects on Venturia inaequalis of apples. Dihydronaphthoate compounds are also a key structural unit of drugs for treating tuberculosis (Ananthan, S.; Faaleolea, E.R.; Goldman, R.C.; Hobrath, J.V.; Kwong, C.D.; Laughon, B.E.; Maddry, J.A.; Mehta, A.; Rasmussen, L.; Reynolds, R.C.; et al. Tuberculosis 2009, 89, 334 - 353.). Recently, non - optically active o - hydroxydihydronaphthoate compounds and their preparation methods have been reported in the literature (Shirinian, V.Z.; Lvov, A.G.; Yadykov, A.V.; Yaminova, L.V.; Kachala, V.V.; Markosyan, A.I. Org. Lett. 2016, 18, 6260 - 6263; Yadykov, A.V.; Yaminova, L.V.; Krayushkin, M.M.; Shirinian, V.Z. Adv. Synth. Catal. 2021, 363, 251 - 258.).

[0003] Optically active polymers have shown potential application values in aspects such as molecular recognition, chiral separation, chiral catalysis, data storage, liquid crystal display, and stealth. The preparation of optically active polymers usually uses chiral monomers as raw materials and is obtained through free radical initiation or anionic and cationic initiation polymerization or polycondensation reactions. Optically active polymers can also be prepared by derivatizing polymers with side chain functional groups using highly optically active chiral monomers with functional groups, such as derivatizing polyamino acids with side chain functional groups. For example, amino acids are a type of chiral small molecule with good optical activity, and regular-structured polymers can be obtained by self-polymerization or graft modification with other macromolecules (Zhou Yuming; Chen Xinglan; Yang Yong; Guo Lingxiang, CN201010517707, 2010.10.22).

[0004] O - Hydroxynaphthalenedicarboxylate also has functional groups such as hydroxyl, formate, and alkenyl, and is a type of highly functionalized compound. In order to prepare highly optically active O - hydroxynaphthalenedicarboxylate compounds, provide new candidate compounds for the development of new drugs and pesticides, and provide highly active monomer compounds or side chain modification molecules for the preparation of optically active polymers. The present invention designs a type of highly optically active O - hydroxynaphthalenedicarboxylate compounds and prepares such highly optically active O - hydroxynaphthalenedicarboxylate compounds through the asymmetric 6π cyclization reaction of triaryl divinyl ketone. The reaction raw materials are simple and easy to obtain, and the operation is simple. The product yield is as high as 95%, the stereoselectivity is good (er up to 98:2), and the substrate has a certain applicability. The synthesized compounds are a type of very important, highly functionalized, highly optically active O - hydroxynaphthalenedicarboxylate compounds, which can be used for polycondensation to prepare optically active polymers or as highly optically active molecules for modifying side chain functionalized polymers. It is also expected to be used as drug and pesticide molecules or their active structural units, or applied to the synthesis of drug and pesticide molecules. Summary of the Invention

[0005] The purpose of the present invention is to provide a type of highly optically active O - hydroxynaphthalenedicarboxylate compounds that can be used as monomers of optically active polymers and their preparation methods. Such compounds are a type of very important highly optically active O - hydroxynaphthalenedicarboxylate compounds that can be used as monomers of optically active polymers. The preparation method of the present invention uses triaryl divinyl ketone as the raw material and chiral pyridine bisoxazoline rare earth complex as the asymmetric catalyst. The raw materials and catalysts are simple and easy to obtain, and do not require cumbersome operations, and it is a method suitable for large-scale preparation.

[0006] The technical solution of the present invention is as follows:

[0007] Highly optically active O - hydroxynaphthalenedicarboxylate compounds (Formula [1]) and their preparation methods. Highly optically active O - hydroxynaphthalenedicarboxylate compounds are obtained by reacting triaryl divinyl ketone under the catalysis of chiral pyridine bisoxazoline rare earth complex.

[0008]

[0009] In the above reaction formula:

[0010] R represents an alkyl group, cycloalkyl group, or cycloalkylalkyl group having 1 to 6 carbon atoms.

[0011] Ar 1 and Ar 2 represent phenyl, alkylphenyl, alkoxyphenyl, dialkylphenyl, dialkoxyphenyl, trialkylphenyl, trialkoxyphenyl having 6 to 12 carbon atoms, and phenyl substituted with fluorine, chlorine, bromine, iodine, nitro, cyano, trifluoromethyl, or mesyl; biphenyl, furan, and thiophenyl; Ar 1 and Ar 2 may be the same or different.

[0012] RE is Ce, La, Tb, Sm, Pr, Eu, Gd, Ho, Er, etc.

[0013] The alkyl group mentioned above refers to a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, etc. A straight-chain or branched-chain alkyl group having 1 to 4 carbon atoms is preferred, and a straight-chain alkyl group having 1 to 2 carbon atoms is particularly preferred.

[0014] The cycloalkyl group mentioned above refers to a cyclic alkyl group having 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc., and cyclopropyl, cyclopentyl, cyclohexyl are preferred.

[0015] The cycloalkylalkyl group mentioned above refers to a cyclic alkyl group having 4 to 6 carbon atoms, such as cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclopropylethyl, cyclobutylethyl, cyclopropylpropyl, etc., and cyclopropylmethyl, cyclopentylmethyl are preferred.

[0016] The aryl group mentioned refers to an aryl group having 6 to 10 carbon atoms. Preferred are phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-trifluoromethylphenyl, m-trifluoromethylphenyl, p-trifluoromethylphenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, o-fluorophenyl, m-fluorophenyl, p-fluorophenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-bromophenyl, m-bromophenyl, p-bromophenyl, o-nitrophenyl, m-nitrophenyl, p-nitrophenyl, o-cyanophenyl, m-cyanophenyl, p-cyanophenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 2,3-dimethoxyphenyl, 2,4-dimethoxyphenyl, 2,5-dimethoxyphenyl, 2,6-dimethoxyphenyl, 2,3,4-trimethylphenyl, 2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4-trimethoxyphenyl, 2,4,6-trimethoxyphenyl, 3,4,5-trimethoxyphenyl, etc.

[0017] The prepared highly optically active o-hydroxydihydronaphthoate compounds, such as the following twenty-three compounds 1a to 1w:

[0018] 1a: R = Me, Ar 1 = 4-MeOC6H4, Ar 2 = 4-CF3C6H4;

[0019] 1b: R = Me, Ar 1 = 4-MeOC6H4, Ar 2 = 4-MeSO2C6H4;

[0020] 1c: R = Me, Ar 1 = 4-MeOC6H4, Ar 2 = 4-O2NC6H4;

[0021] 1d: R = Me, Ar 1 = 4-MeOC6H4, Ar 2 = 4-NCC6H4;

[0022] 1e: R = Me, Ar 1 = 4-MeOC6H4, Ar 2 = 4-ClC6H4;

[0023] 1f: R = Me, Ar 1 = 4-MeOC6H4, Ar 2 = 4-MeOC6H4;

[0024] 1g: R = Me, Ar 1 = 4-MeOC6H4, Ar 2 = 4-Me2CHC6H4;

[0025] 1h: R = Me, Ar 1 = 4-MeOC6H4, Ar 2 = 4-MeC6H4;

[0026] 1i: R = Me, Ar 1 = 4-MeOC6H4, Ar 2 = 4-PhC6H4;

[0027] 1j: R = Me, Ar 1 = 4-MeOC6H4, Ar 2 = Ph;

[0028] 1k: R = Me, Ar 1 = 4-MeOC6H4, Ar 2 = Furan-2-yl;

[0029] 1l: R = Me, Ar 1 = 3,4-(MeO)2C6H3, Ar 2 = 4-ClC6H4;

[0030] 1m: R = Me, Ar 1 = 3,4-(MeO)2C6H3, Ar 2 = 3-ClC6H4;

[0031] 1n: R = Me, Ar 1 = 3,4-(MeO)2C6H3, Ar 2 = 2-ClC6H4;

[0032] 1o: R = Me, Ar 1 = 3,4-(MeO)2C6H3, Ar 2 = 2-BrC6H4;

[0033] 1p: R = Me, Ar 1 = 3,4-(MeO)2C6H3, Ar 2 = 4-BrC6H4;

[0034] 1q: R = Me, Ar 1 = 3,4-(MeO)2C6H3, Ar 2 = 4-FC6H4;

[0035] 1r: R = Me, Ar 1 = 3,4-(MeO)2C6H3, Ar 2 = 4-PhC6H4;

[0036] 1s: R = Me, Ar1 = 3,4-(MeO)2C6H3, Ar 2 = 4-MeC6H4;

[0037] 1t: R = Me, Ar 1 = 3,4-(MeO)2C6H3, Ar 2 = 3,4-Me2C6H3;

[0038] 1u: R = Me, Ar 1 = 3,4-(MeO)2C6H3, Ar 2 = Ph;

[0039] 1v: R = Me, Ar 1 = Ph, Ar 2 = 4-ClC6H4;

[0040] 1w: R = Me, Ar 1 = 4-ClC6H4, Ar 2 = 4-ClC6H4;

[0041] The above preparation method is usually to prepare by catalyzing the reaction of triaryl divinyl ketone in 1,2-dichloroethane or chloroform with a chiral pyridine bisoxazoline rare earth complex.

[0042] In the above preparation method, the structure of the chiral pyridine bisoxazoline ligand is as shown in the formula Pybox.

[0043] In the above preparation method, the rare earth trifluoromethanesulfonate is Ce, La, Tb, Sm, Pr, Eu, Gd, Ho, Er trifluoromethanesulfonate, and can be purchased through commercial channels.

[0044] In the above preparation method, the raw material triaryl divinyl ketone can be prepared according to the literature method.

[0045] In the above preparation method, the chiral pyridine bisoxazoline ligand Pybox can be synthesized according to the literature method or purchased through commercial channels.

[0046] In the above preparation method, the solvents usually used are 1,2-dichloroethane, chloroform, dichloromethane, chlorobenzene, tetrahydrofuran, benzene, toluene, xylene, trifluoromethylbenzene or a mixture thereof.

[0047] In the above preparation method, it is usually prepared by stirring and reacting under the conditions of -40°C to 80°C.

[0048] Advantages and positive effects of the present invention:

[0049] This method can synthesize highly optically active o - hydroxy - 1,2 - dihydronaphthalene - 2 - carboxylates simply and efficiently. This synthetic method has the advantages of high yield, good stereoselectivity, certain substrate applicability, simple reaction, and easily available raw materials. As a novel highly optically active o - hydroxy - 1,2 - dihydronaphthalene - 2 - carboxylate, the product can be used as a monomer for optically active polymers and is also expected to be applied in the research and development of drugs and pesticides. Detailed implementation manners

[0050] The present invention will be further illustrated by the following examples, which do not limit the present invention within the scope of the described examples.

[0051] Example 1

[0052] Synthesis of optically active 3 - hydroxy - 6,7 - dimethoxy - 4 - arylmethylene - 1 - aryl - 1,4 - dihydronaphthalene - 2 - carboxylate 1 (general method)

[0053] Under nitrogen, chiral bis - oxazoline Pybox (56.3 mg, 0.108 mmol), Ce(OTf)3 (52.9 mg, 0.09 mmol) and 1,2 - dichloroethane (DCE) (1 mL) were added to a pre - dried reaction tube and stirred overnight at room temperature. Triaryl divinyl ketone (Formula 2) (0.3 mmol) was dissolved in DCE (1 mL) and added to the above reaction tube by syringe. The reaction mixture was stirred at 0 °C for 48 h. After concentration, the residue was separated by silica gel column chromatography, eluted with ethyl acetate (EA) and petroleum ether (PE) (1:5 to 1:2, v / v) as the eluent to obtain the target product (Formula 1). The characterization data of the product are as follows:

[0054] (R,E) - Methyl 3 - hydroxy - 6,7 - dimethoxy - 4 - (4 - methoxybenzylidene) - 1 - (4 - trifluoromethylphenyl) - 1,4 - dihydronaphthalene - 2 - carboxylate (1a)

[0055] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.69 (PE / EA = 2 / 1, v / v).

[0056] Yellow crystals, m.p. 93.3 - 93.7 °C; 111 mg, yield 70%, 82% ee; HPLC

[0057] (Daicel Chiralpak OD - H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 16 °C):

[0058] t R1 (minor) = 10.2 min, t R2 (major) = 15.2 min; [α] 20 D = +275 (c = 0.82, CHCl3)

[0059] (82% ee). 1 1H NMR (400 MHz, CDCl3) δ 12.62 (s, 1H), 7.52 (d, J = 4.0 Hz, 2H), 7.50 (s, 1H), 7.46–7.39 (m, 4H), 6.97 (s, 1H), 6.86 (d, J = 8.7 Hz, 2H), 6.63 (s, 1H), 5.02 (s, 1H), 3.82 (s, 3H), 3.81 (s, 3H), 3.79 (s, 3H), 3.42 (s, 3H). 13 13C NMR (101 MHz, CDCl3) δ 172.2, 168.2, 159.8, 149.7, 149.2, 147.1, 132.1, 131.2, 129.2, 128.84, 128.79 (q J = 32.4 Hz), 127.7, 127.5, 125.8 (q, J = 3.6 Hz), 123.3, 121.68 (q, J = 263.5 Hz), 114.0, 111.1, 110.6, 100.3, 55.9, 55.52, 55.49, 52.1, 45.7. 19 19F NMR (376 MHz, CDCl3) δ -62.4.

[0060] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(4-(methylsulfonyl)phenyl)-1,4-dihydronaphthalene-2-carboxylate (1b)

[0061] Column chromatography separation conditions (PE / EA = 3 / 1, v / v). R f = 0.43 (PE / EA = 1 / 1, v / v).

[0062] Yellow crystals, m.p. 95.4–96.6 °C; 85 mg, yield 53%, 60% ee; HPLC

[0063] (Daicel Chiralpak OD-H, n hexane / i PrOH = 85:15, 1.0 mL / min, T = 24 °C):

[0064] tR1 (minor) = 29.8 min, t R2 (major) = 34.7 min; [α] 20 D = +167 (c = 1.81,

[0065] CHCl3). 1 1H NMR (400 MHz, CDCl3) δ 12.63 (s, 1H), 7.82 (d, J = 8.4 Hz, 2H), 7.54 (s, 1H), 7.52 (d, J = 8.4 Hz, 2H), 7.42 (d, J = 8.6 Hz, 2H), 6.98 (s, 1H), 6.86 (d, J = 8.7 Hz, 2H), 6.62 (s, 1H), 5.05 (s, 1H), 3.82 (s, 3H), 3.81 (s, 3H), 3.78 (s, 3H), 3.42 (s, 3H), 3.02 (s, 3H). 13 13C NMR (101 MHz, CDCl3) δ 172.0, 168.3, 159.8, 152.0, 149.2, 147.2, 138.7, 131.6, 131.2, 129.5, 128.7, 128.4, 128.0, 127.3, 123.4, 114.1, 111.2, 110.6, 100.0, 55.9, 55.5, 52.1, 45.8, 44.6.

[0066] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(4-nitrophenyl)-1,4-dihydronaphthalene-2-carboxylate (1c)

[0067] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.33 (PE / EA = 3 / 1, v / v).

[0068] Yellow crystals, m.p. 88.4–88.9 °C; 27 mg, yield 18%, 75% ee; HPLC

[0069] (Daicel Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 16 °C):

[0070] t R1 (minor) = 23.3 min, t R2 (major) = 33.0 min; [α] 20D = +342 (c = 0.25,

[0071] CHCl3) (75% ee). 1 1H NMR (400 MHz, CDCl3) δ 12.63 (s, 1H), 8.11 (d, J =

[0072] 8.8 Hz, 2H), 7.54 (s, 1H), 7.48 (d, J = 8.7 Hz, 2H), 7.42 (d, J = 8.7 Hz, 2H), 6.98 (s, 1H), 6.86 (d, J = 8.8 Hz, 2H), 6.62 (s, 1H), 5.07 (s, 1H), 3.82 (s, 3H), 3.81 (s, 3H), 3.78 (s, 3H), 3.42 (s, 3H). 13 13C NMR (101 MHz, CDCl3) δ 172.0, 168.4, 159.8, 153.1, 149.2, 147.3, 146.7, 131.3, 131.2, 129.6, 128.6, 128.2, 127.1, 124.2, 123.4, 114.1, 111.2, 110.5, 99.7, 55.9, 55.49, 55.47, 52.1, 45.7.

[0073] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(4-cyanophenyl)-1,4-dihydronaphthalene-2-carboxylate (1d)

[0074] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.27 (PE / EA = 3 / 1, v / v).

[0075] Yellow crystals, m.p. 67.9–68.7 °C; 33 mg, yield 23%, 79% ee; HPLC

[0076] (Daicel Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 20 °C):

[0077] t R1 (minor) = 25.0 min, t R2 (major) = 35.2 min; [α] 20 D = +387 (c = 1.22, CHCl3)

[0078] (79% ee). 1 1H NMR (400 MHz, CDCl3) δ 12.62 (s, 1H), 7.55 (s, 1H), 7.53 (d,

[0079] J = 1.8 Hz, 2H), 7.43 (d, J = 3.0 Hz, 2H), 7.41 (d, J = 3.5 Hz, 2H), 6.98 (s, 1H), 6.86 (d, J = 8.7 Hz, 2H), 6.60 (s, 1H), 5.01 (s, 1H), 3.82 (s, 3H), 3.81 (s, 3H), 3.78 (s, 3H), 3.42 (s, 3H). 13 13C NMR (101 MHz, CDCl3) δ 172.0, 168.4, 159.8, 151.1, 149.2, 147.2, 132.7, 131.5, 131.2, 129.5, 128.7, 128.2, 127.2, 123.4, 119.0, 114.1, 111.1, 110.6, 110.4, 99.9, 55.9, 55.51, 55.50, 52.1, 45.9.

[0080] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(4-chlorophenyl)-1,4-dihydronaphthalene-2-carboxylate (1e)

[0081] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.48 (PE / EA = 3 / 1, v / v).

[0082] Yellow crystals, m.p. 75.8–76.4 °C; 82 mg, yield 62%, 92% ee; HPLC

[0083] (Daicel Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 18 °C):

[0084] t R1 (minor) = 11.8 min, t R2 (major) = 17.2 min; [α] 20 D = +316 (c = 0.98,

[0085] CHCl3) (94% ee). 11H NMR (400 MHz, CDCl3) δ 12.61 (s, 1H), 7.51 (s, 1H),

[0086] 7.42 (d, J = 8.8 Hz, 2H), 7.26 (d, J = 8.6 Hz, 2H), 7.21 (d, J = 8.5 Hz, 2H), 6.96 (s, 1H), 6.86 (d, J = 8.7 Hz, 2H), 6.63 (s, 1H), 4.94 (s, 1H), 3.81 (s, 6H), 3.78 (s, 3H), 3.42 (s, 3H). 13 13C NMR (101 MHz, CDCl3) δ 172.2, 167.9, 159.7, 149.1, 146.9, 144.2, 132.6, 132.2, 131.2, 128.90, 128.85, 128.7, 127.6, 123.2, 114.0, 111.1, 110.6, 100.6, 55.9, 55.48, 55.45, 52.0, 45.3.

[0087] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(4-methoxyphenyl)-1,4-dihydronaphthalene-2-carboxylate (1f)

[0088] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.39 (PE / EA = 3 / 1, v / v).

[0089] Yellow crystals, m.p. 69.8–70.6 °C; 51 mg, yield 70%, 61% ee; HPLC

[0090] (Daicel Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 19 °C):

[0091] t R1 (minor) = 13.1 min, t R2 (major) = 18.8 min; [α] 20 D = +472 (c = 1.05,

[0092] CHCl3) (61% ee). 1 1H NMR (400 MHz, CDCl3) δ 12.58 (s, 1H), 7.48 (s,

[0093] 1H NMR (400 MHz, CDCl3) δ 12.59 (s, 1H), 7.49 (s, 1H), 7.45 (d, J = 8.4 Hz, 2H), 7.24 (d, J = 8.4 Hz, 2H), 6.94 (s, 1H), 6.85 (d, J = 8.4 Hz, 2H), 6.78 (d, J = 8.3 Hz, 2H), 6.66 (s, 1H), 4.92 (s, 1H), 3.81 (s, 6H), 3.78 (s, 3H), 3.74 (s, 3H), 3.41 (s, 3H). 13 13C NMR (101 MHz, CDCl3) δ 172.5, 167.7, 159.6, 158.2, 149.0, 146.7, 137.8, 133.6, 131.2, 129.1, 128.4, 128.3, 128.0, 123.2, 114.1, 114.0, 111.0, 110.6, 101.3, 55.9, 55.49, 55.47, 55.3, 51.9, 45.1.

[0094] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(4-isopropylphenyl)-1,4-dihydronaphthalene-2-carboxylate (1 g)

[0095] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.55 (PE / EA = 3 / 1, v / v).

[0096] Yellow crystals, m.p. 75.9–76.4 °C; 97 mg, yield 65%, 87% ee; HPLC

[0097] (Daicel Chiralpak OD-H, n hexane / i iPrOH = 95:5, 1.0 mL / min, T = 24 °C):

[0098] t R1 (minor) = 8.4 min, t R2 (major) = 12.1 min; [α] 20 D = +303 (c = 1.10, CHCl3)

[0099] (87% ee). 1 1H NMR (400 MHz, CDCl3) δ 12.59 (s, 1H), 7.49 (s, 1H), 7.45 (d,

[0100] J = 8.6 Hz, 2H), 7.24 (d, J = 8.2 Hz, 2H), 7.10 (d, J = 8.2 Hz, 2H), 6.96 (s, 1H), 6.86 (d, J = 8.8 Hz, 2H), 6.68 (s, 1H), 4.95 (s, 1H), 3.82 (s, 6H), 3.79 (s, 3H), 3.42 (s, 3H), 2.84 (hept, J = 6.9 Hz, 1H), 1.21 (d, J = 6.9 Hz, 6H). 13 C NMR (101 MHz, CDCl3) δ 172.5, 167.7, 159.6, 149.0, 146.8, 146.7, 142.8, 133.6, 131.2, 129.1, 128.4, 128.1, 127.3, 126.8, 123.3, 113.9, 111.0, 110.7, 101.3, 55.8, 55.5, 55.4, 51.9, 45.5, 33.7, 24.1.

[0101] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(4-methylphenyl)-1,4-dihydronaphthalene-2-carboxylate (1h)

[0102] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.52 (PE / EA = 3 / 1, v / v). Yellow crystals, m.p. 78.5–78.7 °C; 78 mg, yield 55%, 88% ee; HPLC (Daicel Chiralpak OD-H, n hexane / i PrOH =

[0103] 95:5, 1.0 mL / min, T = 20 °C): t R1 (minor) = 9.5 min, t R2 (major) = 13.4 min;

[0104] [α] 20 D = +259 (c = 0.51, CHCl3) (91% ee). 1 H NMR (400 MHz, CDCl3) δ

[0105] 12.62 (s, 1H), 7.50 (s, 1H), 7.44 (d, J = 8.6 Hz, 2H), 7.24 (d, J = 8.1 Hz,

[0106] 2H), 7.07 (d, J = 7.9 Hz, 2H), 6.96 (s, 1H), 6.86 (d, J = 8.8 Hz, 2H), 6.68

[0107] (s, 1H), 4.96 (s, 1H), 3.82 (s, 6H), 3.79 (s, 3H), 3.42 (s, 3H), 2.29 (s, 3H).

[0108] 13 C NMR (101 MHz, CDCl3) δ 172.4, 167.8, 159.5, 149.0, 146.7, 142.7, 136.0, 133.5, 131.2, 129.4, 129.1, 128.4, 128.0, 127.2, 123.2, 113.9, 111.0, 110.6, 101.1, 55.8, 55.5, 55.4, 51.9, 45.5, 21.1.

[0109] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(4-phenylphenyl)-1,4-dihydronaphthalene-2-carboxylate (1i)

[0110] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.56 (PE / EA = 3 / 1, v / v).

[0111] Yellow crystals, m.p. 137.7–137.9 °C; 103 mg, yield 64%, 91% ee; HPLC

[0112] (Daicel Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 19 °C):

[0113] t R1 (minor) = 20.0 min, t R2 (major) = 30.0 min; [α] 20 D = +399 (c = 1.96,

[0114] CHCl3) (93% ee). 1 H NMR (400 MHz, CDCl3) δ 12.68 (s, 1H), 7.58–7.54

[0115] (m, 3H), 7.51 (d, J = 8.2 Hz, 2H), 7.48 (d, J = 8.7 Hz, 2H), 7.45–7.38 (m, 4H), 7.34–7.28 (m, 1H), 7.01 (s, 1H), 6.88 (d, J = 8.7 Hz, 2H), 6.75 (s, 1H), 5.06 (s, 1H), 3.85 (s, 3H), 3.82 (s, 3H), 3.82 (s, 3H), 3.45 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 172.4, 167.9, 159.6, 149.0, 146.8, 144.6, 140.9, 139.3, 133.1, 131.2, 129.0, 128.8, 128.6, 127.9, 127.7, 127.5, 127.2, 127.0, 123.3, 113.9, 111.1, 110.6, 100.9, 55.8, 55.43, 55.38, 51.9, 45.5.

[0116] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-phenyl-1,4-dihydronaphthalene-2-carboxylate (1j)

[0117] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.55 (PE / EA = 3 / 1, v / v).

[0118] Yellow crystals, m.p. 70.0–70.7 °C; 92 mg, yield 67%, 92% ee; HPLC

[0119] (Daicel Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 18 °C):

[0120] t R1 (minor) = 13.8 min, t R2 (major) = 20.5 min; [α] 20 D = +290 (c = 1.48,

[0121] CHCl3) (92% ee). 11H NMR (400 MHz, CDCl3) δ 12.62 (s, 1H), 7.51 (s, 1H), 7.44 (d, J = 8.8 Hz, 2H), 7.33 (d, J = 7.3 Hz, 2H), 7.25 (t, J = 7.9 Hz, 2H), 7.20–7.11 (m, 1H), 6.96 (s, 1H), 6.86 (d, J = 8.8 Hz, 2H), 6.68 (s, 1H), 4.98 (s, 1H), 3.81 (s, 6H), 3.78 (s, 3H), 3.42 (s, 3H). 13 13C NMR (101 MHz, CDCl3) δ 172.4, 167.8, 159.6, 149.0, 146.8, 145.6, 133.2, 131.2, 129.1, 128.7, 128.5, 128.0, 127.4, 126.5, 123.3, 114.0, 111.0, 110.7, 101.0, 55.8, 55.47, 55.45, 51.9, 45.9.

[0122] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(furan-2-yl)-1,4-dihydronaphthalene-2-carboxylate (1k)

[0123] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.58 (PE / EA = 3 / 1, v / v).

[0124] Yellow crystals, m.p. 60.8–61.3 °C; 23 mg, yield 17%, 64% ee; HPLC

[0125] (Daicel Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 16 °C):

[0126] t R1 (minor) = 10.8 min, t R2 (major) = 14.6 min; [α] 20 D = +348 (c = 1.05,

[0127] CHCl3) (64% ee). 11H NMR (400 MHz, CDCl3) δ 12.61 (s, 1H), 7.43 (s, 1H), 7.36 (d, J = 8.6 Hz, 2H), 7.26 (s, 1H), 6.91 (s, 1H), 6.85 (s, 1H), 6.82 (d, J = 8.7 Hz, 2H), 6.21 (dd, J = 3.2, 1.9 Hz, 1H), 5.93 (d, J = 3.2 Hz, 1H), 5.10 (s, 1H), 3.88 (s, 3H), 3.83 (s, 3H), 3.79 (s, 3H), 3.42 (s, 3H). 13 13C NMR (101 MHz, CDCl3) δ 172.3, 168.9, 159.6, 157.1, 148.7, 147.0, 141.6, 131.3, 130.0, 129.1, 128.9, 127.5, 124.0, 113.8, 111.1, 110.8, 110.3, 104.3, 97.8, 55.9, 55.5, 55.4, 52.0, 39.1.

[0128] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(3,4-dimethoxybenzylidene)-1-(4-chlorophenyl)-1,4-dihydronaphthalene-2-carboxylate (1l)

[0129] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.37 (PE / EA = 3 / 1, v / v).

[0130] Yellow crystals, m.p. 144.9–145.2 °C; 138 mg, yield 88%, 93% ee; HPLC

[0131] (Daicel Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 16 °C):

[0132] t R1 (minor) = 22.7 min, t R2 (major) = 28.1 min; [α] 20 D = +375 (c = 1.07,

[0133] CHCl3) (93% ee). 1 1H NMR (400 MHz, CDCl3) δ 12.60 (s, 1H), 7.48 (s,

[0134] 1H NMR (400 MHz, CDCl3) δ 7.97 (d, J = 8.4 Hz, 1H), 7.65 (d, J = 1.7 Hz, 1H), 7.58 (dd, J = 8.4, 1.7 Hz, 1H), 7.26 (d, J = 8.5 Hz, 2H), 7.20 (d, J = 8.6 Hz, 2H), 7.10–7.03 (m, 1H),

[0135] 7.01 (d, J = 1.9 Hz, 1H), 6.99 (s, 1H), 6.82 (d, J = 8.3 Hz, 1H), 6.63 (s, 1H), 4.94 (s, 1H), 3.89 (s, 3H), 3.81 (s, 3H), 3.78 (s, 3H), 3.75 (s, 3H), 3.43 (s, 3H). 13 13C NMR (101 MHz, CDCl3) δ 172.2, 167.9, 149.2, 149.1, 148.8, 146.8, 144.2, 132.7, 132.2, 129.1, 128.9, 128.94, 128.85, 127.8, 123.1, 122.9, 112.6, 111.2, 111.1, 110.6, 100.7, 56.1, 56.0, 55.9, 55.6, 52.0, 45.3.

[0136] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(3,4-dimethoxybenzylidene)-1-(3-chlorophenyl)-1,4-dihydronaphthalene-2-carboxylate (1m)

[0137] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.24 (PE / EA = 3 / 1, v / v).

[0138] Yellow crystals, m.p. 78.4–78.6 °C; 41 mg, yield 26%, 88% ee; HPLC

[0139] (Daicel Chiralpak OD-H, n hexane / i i-PrOH = 95:5, 1.0 mL / min, T = 13 °C):

[0140] t R1 (minor) = 25.9 min, t R2 (major) = 34.1 min; [α] 20 D = +249 (c = 3.20,

[0141] CHCl3). 11H NMR (400 MHz, CDCl3) δ 12.61 (s, 1H), 7.50 (s, 1H), 7.29 (t, J = 1.9 Hz, 1H), 7.22 (dt, J = 7.4, 1.6 Hz, 1H), 7.17 (t, J = 7.6 Hz, 1H), 7.12 (dt, J = 7.7, 1.8 Hz, 1H), 7.07 (dd, J = 8.3, 2.2 Hz, 1H), 7.02 (d, J = 2.0 Hz, 1H), 6.98 (s, 1H), 6.83 (d, J = 8.3 Hz, 1H), 6.63 (s, 1H), 4.94 (s, 1H), 3.89 (s, 3H), 3.82 (s, 3H), 3.80 (s, 3H), 3.74 (s, 3H), 3.42 (s, 3H). 13 13C NMR (101 MHz, CDCl3) δ 172.2, 168.0, 149.2, 149.1, 148.8, 147.6, 146.9, 134.3, 132.4, 130.0, 129.2, 127.8, 127.7, 126.7, 125.6, 123.3, 122.9, 112.4, 111.2, 111.1, 110.6, 100.6, 56.1, 55.93, 55.90, 55.6, 52.0, 45.5.

[0142] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(3,4-dimethoxybenzylidene)-1-(2-chlorophenyl)-1,4-dihydronaphthalene-2-carboxylate (1n)

[0143] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.42 (PE / EA = 3 / 1, v / v).

[0144] Yellow crystals, m.p. 118.4–119.0 °C; 117 mg, yield 75%, 83% ee; HPLC

[0145] (Daicel Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 14 °C):

[0146] t R1 (minor) = 20.5 min, t R2 (major) = 22.4 min; [α] 20 D = +223 (c = 1.02,

[0147] (86% ee) of CHCl3 1 1H NMR (400 MHz, CDCl3) δ 12.67 (s, 1H), 7.52 (s,

[0148] 1H), 7.36 (dd, J = 7.5, 1.8 Hz, 1H), 7.27 (dd, J = 7.8, 2.0 Hz, 1H), 7.12–7.02 (m, 3H), 7.00 (d, J = 1.9 Hz, 1H), 6.97 (s, 1H), 6.95 (s, 1H), 6.79 (d, J = 8.3 Hz, 1H), 5.71 (s, 1H), 3.86 (s, 3H), 3.81 (s, 3H), 3.72 (s, 6H), 3.39 (s, 3H). 13 13C NMR (101 MHz, CDCl3) δ 172.3, 168.0, 149.0, 148.7, 146.7, 143.2, 133.0, 132.6, 129.7, 129.3, 128.6, 128.5, 127.8, 127.5, 127.4, 122.8, 122.6, 112.5, 111.00, 110.96, 110.0, 100.5, 56.0, 55.9, 55.6, 55.4, 51.9, 40.7.

[0149] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(3,4-dimethoxybenzylidene)-1-(2-bromophenyl)-1,4-dihydronaphthalene-2-carboxylate (2o)

[0150] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.45 (PE / EA = 3 / 1, v / v).

[0151] Yellow crystals, m.p. 171.3–171.9 °C; 37 mg, yield 22%, 60% ee; HPLC

[0152] (Daicel Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 17.5 °C):

[0153] t R1 (minor) = 20.5 min, t R2 (major) = 23.4 min; [α] 20 D = +190 (c = 0.23, CHCl3)

[0154] (94% ee). 1 H NMR (400 MHz, CDCl3) δ 12.66 (s, 1H), 7.56 (dd, J = 8.0, 1.3 Hz, 1H), 7.54 (s, 1H), 7.27 (dd, J = 8.1, 1.7 Hz, 1H), 7.14 (td, J = 7.5, 1.3 Hz, 1H), 7.09–7.02 (m, 2H), 7.03–6.97 (m, 2H), 6.97 (s, 1H), 6.80 (d, J = 8.3 Hz, 1H), 5.72 (s, 1H), 3.88 (s, 3H), 3.82 (s, 3H), 3.74 (s, 3H), 3.73 (s, 3H), 3.40 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 172.4, 168.0, 149.1, 148.8, 146.8, 145.1, 133.12, 133.10, 129.4, 128.8, 128.6, 128.2, 127.9, 123.6, 122.9, 122.5, 112.6, 111.1, 111.0, 110.0, 100.8, 56.1, 56.0, 55.7, 55.5, 52.0, 43.4.

[0155] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(3,4-dimethoxybenzylidene)-1-(4-bromophenyl)-1,4-dihydronaphthalene-2-carboxylate (1p)

[0156] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.34 (PE / EA = 3 / 1, v / v). Yellow

[0157] crystals, m.p. 87.6–88.4 °C; 148 mg, yield 87%, 88% ee; HPLC (Daicel

[0158] Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 14 °C): t R1 (minor) =

[0159] 26.2 min, t R2 (major) = 34.2 min; [α] 20 D = +358 (c = 1.10, CHCl3).1 1H NMR

[0160] (400 MHz, CDCl3) δ 12.60 (s, 1H), 7.48 (s, 1H), 7.36 (d, J = 8.5 Hz, 2H), 7.20 (d, J = 8.5 Hz, 2H), 7.06 (d, J = 8.3 Hz, 1H), 7.01 (d, J = 1.9 Hz, 1H), 6.99 (s, 1H), 6.81 (d, J = 8.4 Hz, 1H), 6.62 (s, 1H), 4.92 (s, 1H), 3.88 (s, 3H), 3.80 (s, 3H), 3.77 (s, 3H), 3.74 (s, 3H), 3.42 (s, 3H). 13 13C NMR (101 MHz, CDCl3) δ 172.2, 167.8, 149.2, 149.1, 148.8, 146.8, 144.7, 132.6, 131.7, 129.1, 129.0, 128.9, 127.7, 123.1, 122.9, 120.2, 112.5, 111.1, 111.0, 110.5, 100.6, 56.0, 55.9, 55.8, 55.5, 52.0, 45.3.

[0161] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(3,4-dimethoxybenzylidene)-1-(4-fluorophenyl)-1,4-dihydronaphthalene-2-carboxylate (1q)

[0162] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.33 (PE / EA = 3 / 1, v / v). Yellow

[0163] crystals, m.p. 146.0–146.7 °C; 144 mg, yield 95%, 96% ee; HPLC (Daicel

[0164] Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 13 °C): t R1 (minor) =

[0165] 27.0 min, t R2 (major) = 34.6 min; [α] 20 D = +307 (c = 1.45, CHCl3). 1 1H NMR

[0166] (400 MHz, CDCl3) δ 12.62 (s, 1H), 7.50 (s, 1H), 7.33–7.29 (m, 2H), 7.09 (dd, J = 8.3, 2.0 Hz, 1H), 7.04 (d, J = 2.0 Hz, 1H), 7.02 (s, 1H), 6.94 (t, J = 8.7 Hz, 2H), 6.84 (d, J = 8.3 Hz, 1H), 6.66 (s, 1H), 4.98 (s, 1H), 3.90 (s, 3H), 3.83 (s, 3H), 3.80 (s, 3H), 3.77 (s, 3H), 3.45 (s, 3H). 13 13C NMR (101 MHz, CDCl3) 172.2, 167.7, 161.5 (d, J = 244.5 Hz), 149.15, 149.08, 148.8, 146.7, 141.3 (d, J = 2.6 Hz), 133.0, 129.1, 128.81, 128.76 (d, J = 5.7 Hz), 127.8, 123.1, 122.9, 115.4 (d, J = 21.2 Hz), 112.6, 111.10, 111.06, 110.5, 101.0, 56.0, 55.9, 55.8, 55.5, 51.9, 45.1. 19 19F NMR (376 MHz, CDCl3) δ -116.8.

[0167] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(3,4-dimethoxybenzylidene)-1-(4-phenylphenyl)-1,4-dihydronaphthalene-2-carboxylate (1r)

[0168] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.34 (PE / EA = 3 / 1, v / v). Yellow

[0169] crystals, m.p. 91.5–91.8 °C; 128 mg, yield 76%, 94% ee; HPLC (Daicel

[0170] Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 17.5 °C): t R1 (minor)

[0171] = 32.5 min, t R2 (major) = 39.7 min; [α] 20D = +443 (c = 1.31, CHCl3) (94% ee).

[0172] 1 H NMR (400 MHz, CDCl3) δ 12.64 (s, 1H), 7.56–7.47 (m, 5H), 7.45–7.36 (m, 4H), 7.35–7.26 (m, 1H), 7.11 (dd, J = 8.4, 1.6 Hz, 1H), 7.06 (d, J = 1.9 Hz, 1H), 7.02 (s, 1H), 6.83 (d, J = 8.3 Hz, 1H), 6.72 (s, 1H), 5.03 (s, 1H), 3.89 (s, 3H), 3.84 (s, 3H), 3.81 (s, 3H), 3.76 (s, 3H), 3.44 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 172.4, 167.8, 149.14, 149.11, 148.8, 146.8, 144.7, 140.9, 139.4, 133.2, 129.3, 128.8, 128.7, 128.2, 127.8, 127.5, 127.3, 127.0, 123.3, 123.0, 112.6, 111.2, 111.1, 110.7, 101.1, 56.1, 56.0, 55.9, 55.6, 52.0, 45.6.

[0173] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(3,4-dimethoxybenzylidene)-1-(4-methylphenyl)-1,4-dihydronaphthalene-2-carboxylate (1s)

[0174] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.37 (PE / EA = 3 / 1, v / v). Yellow

[0175] crystals, m.p. 77.6–77.9 °C; 108 mg, yield 72%, 93% ee; HPLC (Daicel

[0176] Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 17 °C): t R1 (minor) =

[0177] 19.6 min, t R2 (major) = 23.5 min; [α] 20D = +305 (c = 1.58, CHCl3) (93% ee). 1 H

[0178] NMR (400 MHz, CDCl3) δ 12.61 (s, 1H), 7.48 (s, 1H), 7.23 (d, J = 8.1 Hz,

[0179] 2H), 7.14–7.02 (m, 4H), 7.00 (s, 1H), 6.82 (d, J = 8.3 Hz, 1H), 6.68 (s, 1H), 4.95 (s, 1H), 3.89 (s, 3H), 3.81 (s, 3H), 3.78 (s, 3H), 3.74 (s, 3H), 3.43 (s, 3H), 2.28 (s, 3H). 13 13C NMR (101 MHz, CDCl3) δ 172.4, 167.6, 149.02, 149.00, 148.7, 146.6, 142.6, 136.0, 133.5, 129.4, 129.2, 128.4, 128.2, 127.2, 123.1, 122.9, 112.5, 111.1, 111.0, 110.6, 101.2, 56.0, 55.9, 55.8, 55.5, 51.9, 45.4, 21.0.

[0180] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(3,4-dimethoxybenzylidene)-1-(3,5-dimethylphenyl)-1,4-dihydronaphthalene-2-carboxylate (1t)

[0181] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.55 (PE / EA = 3 / 1, v / v).

[0182] Yellow crystals, m.p. 69.5–70.5 °C; 162 mg, yield 79%, 88% ee; HPLC

[0183] (Daicel Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 17 °C):

[0184] t R1 (minor) = 18.1 min, t R2 (major) = 24.9 min; [α] 20 D= +145 (c = 2.18, CHCl3)

[0185] (88% ee). 1 1H NMR (400 MHz, CDCl3) δ 12.60 (s, 1H), 7.48 (s, 1H), 7.11–7.04 (m, 2H), 6.97 (s, 1H), 6.95 (s, 2H), 6.83 (d, J = 8.3 Hz, 1H), 6.80 (s, 1H), 6.67 (s, 1H), 4.91 (s, 1H), 3.89 (s, 3H), 3.82 (s, 3H), 3.80 (s, 3H), 3.73 (s, 3H), 3.43 (s, 3H), 2.24 (s, 6H). 13 13C NMR (101 MHz, CDCl3) δ 172.4, 167.7, 149.04, 149.00, 148.8, 146.6, 145.5, 138.1, 133.7, 129.4, 128.5, 128.3, 128.2, 125.3, 123.3, 122.9, 112.4, 111.2, 111.1, 110.6, 101.3, 56.1, 55.9, 55.8, 55.6, 51.9, 45.7, 21.6.

[0186] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(3,4-dimethoxybenzylidene)-1-phenyl-1,4-dihydronaphthalene-2-carboxylate (1u)

[0187] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.39 (PE / EA = 3 / 1, v / v). Yellow crystals, m.p. 163.0–163.7 °C; 110 mg, yield 75%, 90% ee; HPLC (Daicel Chiralpak OD-H,

[0188] n hexane / i PrOH = 95:5, 1.0 mL / min, T = 17 °C): t R1 (minor) = 24.1 min,

[0189] t R2 (major) = 31.5 min; [α] 20 D = +358 (c = 1.06, CHCl3) (96% ee). 1 1H NMR

[0190] (400 MHz, CDCl3) δ 12.62 (s, 1H), 7.49 (s, 1H), 7.34 (d, J = 7.9 Hz, 2H), 7.23

[0191] (d, J = 7.7 Hz, 2H), 7.18–7.12 (m, 1H), 7.09 (dd, J = 8.3, 1.9 Hz, 1H), 7.04 (d, J = 1.9 Hz, 1H), 7.00 (s, 1H), 6.82 (d, J = 8.3 Hz, 1H), 6.68 (s, 1H), 4.98 (s, 1H), 3.88 (s, 3H), 3.81 (s, 3H), 3.77 (s, 3H), 3.73 (s, 3H), 3.43 (s, 3H). 13 13C NMR (101 MHz, CDCl3) δ 172.3, 167.7, 149.03, 148.97, 148.7, 146.6, 145.5, 133.3, 129.2, 128.6, 128.5, 128.1, 127.4, 126.4, 123.1, 122.9, 112.5, 111.1, 111.0, 110.6, 101.1, 56.0, 55.9, 55.8, 55.5, 51.9, 45.8.

[0192] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-benzylidene-1-(4-chlorophenyl)-1,4-dihydronaphthalene-2-carboxylate (1v)

[0193] Column chromatography separation conditions (PE / EA = 4 / 1, v / v), R f = 0.79 (PE / EA = 3 / 1, v / v).

[0194] Yellow crystals, m.p. 76.3–77.1 °C, 46 mg, yield 33%, 60% ee. HPLC

[0195] (Daicel Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 11 °C):

[0196] t R1 (minor) = 11.09 min, t R2 (major) = 14.72 min, [α] 20 D = +192 (c = 0.8,

[0197] CHCl3). 11H NMR (400 MHz, CDCl3) δ 12.60 (s, 1H), 7.59 (s, 1H), 7.47–7.40 (m, 2H), 7.33 (t, J = 7.4 Hz, 2H), 7.31–7.19 (m, 5H), 6.80 (s, 1H), 6.62 (s, 1H), 4.95 (s, 1H), 3.80 (s, 3H), 3.79 (s, 3H), 3.31 (s, 3H). 13 13C NMR (100 MHz, CDCl3) δ 172.2, 167.5, 149.2, 146.9, 144.1, 137.0, 132.6, 132.3, 129.5, 129.1, 128.9, 128.8, 128.7, 128.1, 122.8, 111.3, 110.5, 101.1, 55.9, 55.3, 52.1, 45.3.

[0198] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(4-chlorobenzylidene)-1-(4-chlorophenyl)-1,4-dihydronaphthalene-2-carboxylate (1w) Column chromatography separation conditions (PE / EA = 4 / 1, v / v), R f = 0.68 (PE / EA = 2 / 1, v / v). Yellow

[0199] crystals, m.p. 67.3–68.2 °C, 112 mg, yield 75%, 70% ee. HPLC (Daicel

[0200] Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 15 °C): t R1 (minor) =

[0201] 12.52 min, t R2 (major) = 20.15 min, [α] 20 D = +247 (c = 1.0, CHCl3). 1 1H NMR

[0202] (400 MHz, CDCl3) δ 12.59 (s, 1H), 7.48 (s, 1H), 7.38 (d, J = 8.2 Hz, 2H), 7.30 (d, J = 8.2 Hz, 2H), 7.23 (s, 4H), 6.78 (s, 1H), 6.63 (s, 1H), 4.95 (s, 1H), 3.81 (s, 3H), 3.78 (s, 3H), 3.38 (s, 3H).13 13C NMR (100 MHz, CDCl3) δ 172.2, 167.2, 149.4, 147.0, 143.9, 135.3, 133.9, 132.9, 132.3, 130.9, 129.6, 128.9, 128.8, 128.7, 127.4, 122.4, 111.1, 110.6, 101.2, 55.9, 55.4, 52.1, 45.3.

[0203] Example 2

[0204] Synthesis of Optically Active 3-Hydroxy-6,7-dimethoxy-4-arylmethylene-1-aryl-1,4-dihydronaphthalene-2-carboxylates 1 (General Method)

[0205] Under nitrogen, chiral bisoxazoline Pybox (56.3 mg, 0.108 mmol), Ce(OTf)3 (52.9 mg, 0.09 mmol) and chloroform (1 mL) were added to a pre-dried reaction tube and stirred overnight at room temperature. Triaryldivinyl ketone (Formula 2) (0.3 mmol) was dissolved in chloroform (1 mL) and added to the above reaction tube by syringe. The reaction mixture was stirred at 0 °C for 48 h. After concentration, the residue was separated by silica gel column chromatography, eluted with ethyl acetate (EA) and petroleum ether (PE) (1:5 to 1:2, v / v) as the eluent to obtain the target product (Formula 1). The characterization data of the product are as follows:

[0206] (R,E)-Methyl 3-Hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(4-trifluoromethylphenyl)-1,4-dihydronaphthalene-2-carboxylate (1a)

[0207] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.69 (PE / EA = 2 / 1, v / v).

[0208] Yellow crystals, m.p. 93.3–93.7 °C; 44 mg, yield 27%, 91% ee, HPLC

[0209] (Daicel Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 16 °C):

[0210] t R1 (minor) = 10.2 min, t R2 (major) = 15.2 min; [α]20 D = +275 (c = 0.82, CHCl3)

[0211] (82% ee).

[0212] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(4-nitrophenyl)-1,4-dihydronaphthalene-2-carboxylate (1c)

[0213] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.33 (PE / EA = 3 / 1, v / v).

[0214] Yellow crystals, m.p. 88.4–88.9 °C; 16 mg, yield 11%, 69% ee; HPLC

[0215] (Daicel Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 16 °C):

[0216] t R1 (minor) = 23.3 min, t R2 (major) = 33.0 min; [α] 20 D = +342 (c = 0.25,

[0217] CHCl3) (75% ee).

[0218] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(4-cyanophenyl)-1,4-dihydronaphthalene-2-carboxylate (1d)

[0219] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.27 (PE / EA = 3 / 1, v / v).

[0220] Yellow crystals, m.p. 67.9–68.7 °C; 18 mg, yield 12%, 88% ee; HPLC

[0221] (Daicel Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 20 °C):

[0222] t R1 (minor) = 25.0 min, t R2 (major) = 35.2 min; [α] 20 D = +387 (c = 1.22, CHCl3)

[0223] (79% ee).

[0224] (R,E)-3-Hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(4-chlorophenyl)-1,4-dihydronaphthalene-2-carboxylic acid methyl ester (1e)

[0225] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.48 (PE / EA = 3 / 1, v / v).

[0226] Yellow crystals, m.p. 75.8–76.4 °C; 46 mg, yield 31%, 94% ee; HPLC

[0227] (Daicel Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 18 °C):

[0228] t R1 (minor) = 11.8 min, t R2 (major) = 17.2 min; [α] 20 D = +316 (c = 0.98,

[0229] CHCl3) (94% ee).

[0230] (R,E)-3-Hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(4-methoxyphenyl)-1,4-dihydronaphthalene-2-carboxylic acid methyl ester (1f)

[0231] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.39 (PE / EA = 3 / 1, v / v).

[0232] Yellow crystals, m.p. 69.8–70.6 °C; 41 mg, yield 56%, 83% ee; HPLC

[0233] (Daicel Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 19 °C):

[0234] t R1 (minor) = 13.1 min, t R2 (major) = 18.8 min; [α] 20 D = +472 (c = 1.05,

[0235] CHCl3) (61% ee).

[0236] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(4-isopropylphenyl)-1,4-dihydronaphthalene-2-carboxylate (1g)

[0237] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.55 (PE / EA = 3 / 1, v / v).

[0238] Yellow crystals, m.p. 75.9–76.4 °C; 77 mg, yield 51%, 91% ee; HPLC

[0239] (Daicel Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 24 °C):

[0240] t R1 (minor) = 8.4 min, t R2 (major) = 12.1 min; [α] 20 D = +303 (c = 1.10, CHCl3)

[0241] (87% ee).

[0242] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(4-methylphenyl)-1,4-dihydronaphthalene-2-carboxylate (1h)

[0243] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.52 (PE / EA = 3 / 1, v / v).

[0244] Yellow crystals, m.p. 78.5–78.7 °C; 55 mg, yield 39%, 91% ee; HPLC

[0245] (Daicel Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 20 °C):

[0246] t R1 (minor) = 9.5 min, t R2 (major) = 13.4 min; [α] 20 D = +259 (c = 0.51,

[0247] CHCl3) (91% ee).

[0248] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(4-phenylphenyl)-1,4-dihydronaphthalene-2-carboxylate (1i)

[0249] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.56 (PE / EA = 3 / 1, v / v).

[0250] Yellow crystals, m.p. 137.7–137.9 °C; 70 mg, yield 44%, 93% ee; HPLC

[0251] (Daicel Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 19 °C):

[0252] t R1 (minor) = 20.0 min, t R2 (major) = 30.0 min; [α] 20 D = +399 (c = 1.96,

[0253] CHCl3) (93% ee).

[0254] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-phenyl-1,4-dihydronaphthalene-2-carboxylate (1j)

[0255] Column chromatography separation conditions (PE / EA=4 / 1, v / v). f =0.55(PE / EA=3 / 1,v / v).

[0256] Yellow crystals, mp70.0–70.7℃; 58mg, yield 42%, 94%ee; HPLC

[0257] (Daicel Chiralpak OD-H, n hexane / i PrOH=95:5, 1.0mL / min, T=18℃):

[0258] t R1 (minor)=13.8min,t R2 (major) = 20.5min; [α] 20 D = +290 (c = 1.48,

[0259] CHCl3)(92%ee).

[0260] (R,E)-3-Hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(furan-2-yl)-1,4-dihydronaphthalene-2-carboxylic acid methyl ester (1k)

[0261] Column chromatography separation conditions (PE / EA=4 / 1, v / v). f =0.58(PE / EA=3 / 1,v / v).

[0262] Yellow crystals,mp60.8–61.3℃;10mg,yield 7%,81%ee;HPLC

[0263] (Daicel Chiralpak OD-H, n hexane / i PrOH=95:5, 1.0mL / min, T=16℃):

[0264] t R1 (minor)=10.8min,t R2 (major) = 14.6min; [α] 20 D = +348 (c = 1.05,

[0265] CHCl3)(64%ee).

[0266] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(3,4-dimethoxybenzylidene)-1-(4-chlorophenyl)-1,4-dihydronaphthalene-2-carboxylate (1l)

[0267] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.37 (PE / EA = 3 / 1, v / v).

[0268] Yellow crystals, m.p. 144.9–145.2 °C; 129 mg, yield 82%, 96% ee; HPLC

[0269] (Daicel Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 16 °C):

[0270] t R1 (minor) = 22.7 min, t R2 (major) = 28.1 min; [α] 20 D = +375 (c = 1.07,

[0271] CHCl3) (93% ee).

[0272] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(3,4-dimethoxybenzylidene)-1-(2-chlorophenyl)-1,4-dihydronaphthalene-2-carboxylate (1n)

[0273] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.42 (PE / EA = 3 / 1, v / v).

[0274] Yellow crystals, m.p. 118.4–119.0 °C; 71 mg, yield 45%, 86% ee; HPLC

[0275] (Daicel Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 14 °C):

[0276] t R1 (minor) = 20.5 min, t R2 (major) = 22.4 min; [α]20 D = +223 (c = 1.02,

[0277] CHCl3) (86% ee).

[0278] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(3,4-dimethoxybenzylidene)-1-(2-bromophenyl)-1,4-dihydronaphthalene-2-carboxylate (2o)

[0279] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.45 (PE / EA = 3 / 1, v / v). 23

[0280] mg, yield 14%, 94% ee; HPLC (Daicel Chiralpak OD-H, n hexane / i PrOH =

[0281] 95:5, 1.0 mL / min, T = 17.5 °C): t R1 (minor) = 20.5 min, t R2 (major) = 23.4 min;

[0282] [α] 20 D = +190 (c = 0.23, CHCl3) (94% ee).

[0283] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(3,4-dimethoxybenzylidene)-1-(4-phenylphenyl)-1,4-dihydronaphthalene-2-carboxylate (1r)

[0284] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.34 (PE / EA = 3 / 1, v / v). Yellow

[0285] crystals, m.p. 91.5–91.8 °C; 100 mg, yield 96%, 96% ee; HPLC (Daicel

[0286] Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 17.5 °C): t R1 (minor)

[0287] = 32.5 min, t R2 (major) = 39.7 min; [α] 20 D = +443 (c = 1.31, CHCl3) (94% ee).

[0288] (R,E)-3-Hydroxy-6,7-dimethoxy-4-(3,4-dimethoxybenzylidene)-1-(4-methylphenyl)-1,4-dihydronaphthalene-2-carboxylic acid methyl ester (1s)

[0289] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.37 (PE / EA = 3 / 1, v / v). Yellow

[0290] crystals, m.p. 77.6–77.9 °C; 100 mg, yield 66%, 96% ee; HPLC (Daicel

[0291] Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 17 °C): t R1 (minor) =

[0292] 19.6 min, t R2 (major) = 23.5 min; [α] 20 D = +305 (c = 1.58, CHCl3) (93% ee).

[0293] (R,E)-3-Hydroxy-6,7-dimethoxy-4-(3,4-dimethoxybenzylidene)-1-(3,5-dimethylphenyl)-1,4-dihydronaphthalene-2-carboxylic acid methyl ester (1t)

[0294] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.55 (PE / EA = 3 / 1, v / v).

[0295] Yellow crystals, m.p. 69.5–70.5 °C; 55 mg, yield 35%, 94% ee; HPLC

[0296] (Daicel Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 17 °C):

[0297] t R1 (minor) = 18.1 min, t R2 (major) = 24.9 min; [α] 20 D = +145 (c = 2.18, CHCl3)

[0298] (88% ee).

[0299] (R,E)-3-Hydroxy-6,7-dimethoxy-4-(3,4-dimethoxybenzylidene)-1-phenyl-1,4-dihydronaphthalene-2-carboxylic acid methyl ester (1u)

[0300] Column chromatography separation conditions (PE / EA = 4 / 1, v / v). R f = 0.39 (PE / EA = 3 / 1, v / v). Yellow

[0301] crystals, m.p. 163.0–163.7 °C; 96 mg, yield 65%, 96% ee; HPLC (Daicel

[0302] Chiralpak OD-H, n hexane / i PrOH = 95:5, 1.0 mL / min, T = 17 °C): t R1 (minor) =

[0303] 24.1 min, t R2 (major) = 31.5 min; [α] 20 D = +358 (c = 1.06, CHCl3) (96% ee). Example 3

[0304] (R,E)-3-Hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(4-trifluoromethylphenyl)-1,4-dihydronaphthalene-2-carboxylic acid methyl ester (1a)

[0305] Under nitrogen, chiral bisoxazoline Pybox (56.3 mg, 0.108 mmol), Ce(OTf)3 (52.9 mg, 0.09 mmol) and chlorobenzene (1 mL) were added to a pre-dried reaction tube and stirred overnight at room temperature. Triaryl divinyl ketone (Formula 2) (0.3 mmol) was dissolved in chlorobenzene (1 mL) and added to the above reaction tube via syringe. The reaction mixture was stirred at 0 °C for 14 h. After concentration, the residue was separated by silica gel column chromatography and eluted with ethyl acetate (EA) and petroleum ether (PE) (1:4, v / v) as the eluent to obtain the target product 1a. 19 mg, yield 12%, 82% ee.

[0306] Example 4

[0307] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(4-trifluoromethylphenyl)-1,4-dihydronaphthalene-2-carboxylate (1a)

[0308] Under nitrogen, chiral bisoxazoline Pybox (56.3 mg, 0.108 mmol), Ce(OTf)3 (52.9 mg, 0.09 mmol) and dichloromethane (1 mL) were added to a pre-dried reaction tube and stirred overnight at room temperature. Triaryl divinyl ketone (Formula 2) (0.3 mmol) was dissolved in dichloromethane (1 mL) and added to the above reaction tube via syringe. The reaction mixture was stirred at 0 °C for 17 h. After concentration, the residue was separated by silica gel column chromatography and eluted with ethyl acetate (EA) and petroleum ether (PE) (1:4, v / v) as the eluent to obtain the target product 1a. 71 mg, yield 45%, 78% ee.

[0309] Example 5

[0310] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(4-trifluoromethylphenyl)-1,4-dihydronaphthalene-2-carboxylate (1a)

[0311] Under nitrogen, chiral bisoxazoline Pybox (56.3 mg, 0.108 mmol), Ce(OTf)3 (52.9 mg, 0.09 mmol) and THF (1 mL) were added to a pre-dried reaction tube and stirred overnight at room temperature. Triaryl divinyl ketone (Formula 2) (0.3 mmol) was dissolved in THF (1 mL) and added to the above reaction tube by syringe. The reaction mixture was stirred at 0 °C for 7 h. After concentration, the residue was separated by silica gel column chromatography, eluted with ethyl acetate (EA) and petroleum ether (PE) (1:4, v / v) as the eluent to obtain the target product 1a. 40 mg, yield 25%, 61% ee.

[0312] Example VI

[0313] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(4-trifluoromethylphenyl)-1,4-dihydronaphthalene-2-carboxylate (1a)

[0314] Under nitrogen, chiral bisoxazoline Pybox (56.3 mg, 0.108 mmol), Ce(OTf)3 (52.9 mg, 0.09 mmol) and a mixture of dichloroethane and chloroform (1 mL, 1:1, v / v) were added to a pre-dried reaction tube and stirred overnight at room temperature. Triaryl divinyl ketone (Formula 2) (0.3 mmol) was dissolved in a mixture of dichloroethane and chloroform (1 mL, 1:1, v / v) and added to the above reaction tube by syringe. The reaction mixture was stirred at 0 °C for 48 h. After concentration, the residue was separated by silica gel column chromatography, eluted with ethyl acetate (EA) and petroleum ether (PE) (1:4, v / v) as the eluent to obtain the target product 1a. 40 mg, yield 25%, 61% ee.

[0315] Example VII

[0316] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(4-trifluoromethylphenyl)-1,4-dihydronaphthalene-2-carboxylate (1a)

[0317] Under nitrogen, chiral bisoxazoline Pybox (56.3 mg, 0.108 mmol), Tb(OTf)3 (54.5 mg, 0.09 mmol) and DCE (1 mL) were added to a pre-dried reaction tube and stirred overnight at room temperature. Triaryl divinyl ketone (Formula 2) (0.3 mmol) was dissolved in DCE (1 mL) and added to the above reaction tube via syringe. The reaction mixture was stirred at 0 °C for 12 h. After concentration, the residue was separated by silica gel column chromatography and eluted with ethyl acetate (EA) and petroleum ether (PE) (1:4, v / v) as the eluent to obtain the target product 1a. 78 mg, yield 49%, 60% ee.

[0318] Example VIII

[0319] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(4-trifluoromethylphenyl)-1,4-dihydronaphthalene-2-carboxylate (1a)

[0320] Under nitrogen, chiral bisoxazoline Pybox (56.3 mg, 0.108 mmol), Eu(OTf)3 (54.0 mg, 0.09 mmol) and DCE (1 mL) were added to a pre-dried reaction tube and stirred overnight at room temperature. Triaryl divinyl ketone (Formula 2) (0.3 mmol) was dissolved in DCE (1 mL) and added to the above reaction tube via syringe. The reaction mixture was stirred at 0 °C for 12 h. After concentration, the residue was separated by silica gel column chromatography and eluted with ethyl acetate (EA) and petroleum ether (PE) (1:4, v / v) as the eluent to obtain the target product 1a. 60 mg, yield 38%, 56% ee.

[0321] Example IX

[0322] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(4-trifluoromethylphenyl)-1,4-dihydronaphthalene-2-carboxylate (1a)

[0323] Under nitrogen, chiral bisoxazoline Pybox (56.3 mg, 0.108 mmol), Gd(OTf)3 (54.5 mg, 0.09 mmol) and DCE (1 mL) were added to a pre-dried reaction tube and stirred overnight at room temperature. Triaryl divinyl ketone (Formula 2) (0.3 mmol) was dissolved in DCE (1 mL) and added to the above reaction tube via syringe. The reaction mixture was stirred at 0 °C for 12 h. After concentration, the residue was separated by silica gel column chromatography and eluted with ethyl acetate (EA) and petroleum ether (PE) (1:4, v / v) as the eluent to obtain the target product 1a. 70 mg, yield 44%, 55% ee.

[0324] Example X

[0325] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(4-trifluoromethylphenyl)-1,4-dihydronaphthalene-2-carboxylate (1a)

[0326] Under nitrogen, chiral bisoxazoline Pybox (56.3 mg, 0.108 mmol), Pr(OTf)3 (44.1 mg, 0.09 mmol) and DCE (1 mL) were added to a pre-dried reaction tube and stirred overnight at room temperature. Triaryl divinyl ketone (Formula 2) (0.3 mmol) was dissolved in DCE (1 mL) and added to the above reaction tube via syringe. The reaction mixture was stirred at 0 °C for 12 h. After concentration, the residue was separated by silica gel column chromatography and eluted with ethyl acetate (EA) and petroleum ether (PE) (1:4, v / v) as the eluent to obtain the target product 1a. 56 mg, yield 35%, 67% ee.

[0327] Example XI

[0328] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(4-trifluoromethylphenyl)-1,4-dihydronaphthalene-2-carboxylate (1a)

[0329] Under nitrogen, chiral bisoxazoline Pybox (56.3 mg, 0.108 mmol), Sm(OTf)3 (53.7 mg, 0.09 mmol) and DCE (1 mL) were added to a pre-dried reaction tube and stirred overnight at room temperature. Triaryl divinyl ketone (Formula 2) (0.3 mmol) was dissolved in DCE (1 mL) and added to the above reaction tube via syringe. The reaction mixture was stirred at 0 °C for 12 h. After concentration, the residue was separated by silica gel column chromatography and eluted with ethyl acetate (EA) and petroleum ether (PE) (1:4, v / v) as the eluent to obtain the target product 1a. 44 mg, yield 28%, 66% ee.

[0330] Example XII

[0331] (R,E)-Methyl 3-hydroxy-6,7-dimethoxy-4-(4-methoxybenzylidene)-1-(4-trifluoromethylphenyl)-1,4-dihydronaphthalene-2-carboxylate (1a)

[0332] Under nitrogen, chiral bisoxazoline Pybox (56.3 mg, 0.108 mmol), La(OTf)3 (52.7 mg, 0.09 mmol) and DCE (1 mL) were added to a pre-dried reaction tube and stirred overnight at room temperature. Triaryl divinyl ketone (Formula 2) (0.3 mmol) was dissolved in DCE (1 mL) and added to the above reaction tube via syringe. The reaction mixture was stirred at 0 °C for 12 h. After concentration, the residue was separated by silica gel column chromatography and eluted with ethyl acetate (EA) and petroleum ether (PE) (1:4, v / v) as the eluent to obtain the target product 1a. 36 mg, yield 23%, 61% ee.

[0333] Example XIII

[0334] Optically active polyester material

[0335] 1.2 g of highly optically active monomer 1q was dissolved in 1,2-dichloroethane, 10 mg of p-toluenesulfonic acid was added, and the mixture was heated to 80 °C for 24 h. Methanol produced during the reaction was removed by evaporation, p-toluenesulfonic acid was removed by washing with water, and the mixture was concentrated and dried to obtain 1.2 g of optically active polyester material. The specific rotation of this material was [α] 20 D = +300 (C = 1 g / 100 mL, 1,2-dichloroethane), the glass transition temperature was 260 °C, and the thermal decomposition temperature was 320 °C

[0336]

Claims

1. A class of highly optically active o - hydroxydihydronaphthoate compounds that can be used as monomers for optically active materials, with the following general structural formula: In formula (1): R represents an alkyl group, cycloalkyl group, cycloalkylalkyl group having 1 to 6 carbon atoms; Ar 1 and Ar 2 represent phenyl, alkylphenyl, alkoxyphenyl, dialkylphenyl, dialkoxyphenyl, trialkylphenyl, trialkoxyphenyl having 6 to 12 carbon atoms, and phenyl substituted with fluorine, chlorine, bromine, iodine, nitro, cyano, trifluoromethyl, methanesulfonyl; biphenyl, furan and thiophenyl; Ar 1 and Ar 2 may be the same or different.

2. The o-hydroxy naphthalenedicarboxylate compound according to claim 1, characterized in that, The o - hydroxydihydronaphthoate compound is selected from one of the following compounds 1a - 1w: 1a: R = Me, Ar 1 = 4-MeOC6H4, Ar 2 = 4-CF3C6H4; 1b: R = Me, Ar 1 = 4-MeOC6H4, Ar 2 = 4-MeSO2C6H4; 1c: R = Me, Ar 1 = 4-MeOC6H4, Ar 2 = 4-O2NC6H4; 1d: R = Me, Ar 1 = 4-MeOC6H4, Ar 2 = 4-NCC6H4; 1e: R = Me, Ar 1 = 4-MeOC6H4, Ar 2 = 4-ClC6H4; 1f: R = Me, Ar 1 = 4-MeOC6H4, Ar 2 = 4-MeOC6H4; 1g: R = Me, Ar 1 = 4-MeOC6H4, Ar 2 = 4-Me2CHC6H4; 1h: R = Me, Ar 1 = 4-MeOC6H4, Ar 2 = 4-MeC6H4; 1i: R = Me, Ar 1 = 4-MeOC6H4, Ar 2 = 4-PhC6H4; 1j: R = Me, Ar 1 = 4-MeOC6H4, Ar 2 = Ph; 1k: R = Me, Ar 1 = 4-MeOC6H4, Ar 2 = Furan-2-yl; 1l: R = Me, Ar 1 = 3,4-(MeO)2C6H3, Ar 2 = 4-ClC6H4; 1m: R = Me, Ar 1 = 3,4-(MeO)2C6H3, Ar 2 = 3-ClC6H4; 1n: R = Me, Ar 1 = 3,4-(MeO)2C6H3, Ar 2 = 2-ClC6H4; 1o: R = Me, Ar 1 = 3,4-(MeO)2C6H3, Ar 2 = 2-BrC6H4; 1p: R = Me, Ar 1 = 3,4-(MeO)2C6H3, Ar 2 = 4-BrC6H4; 1q: R = Me, Ar 1 = 3,4-(MeO)2C6H3, Ar 2 = 4-FC6H4; 1r: R = Me, Ar 1 = 3,4-(MeO)2C6H3, Ar 2 = 4-PhC6H4; 1s: R = Me, Ar 1 = 3,4-(MeO)2C6H3, Ar 2 = 4-MeC6H4; 1t: R = Me, Ar 1 = 3,4-(MeO)2C6H3, Ar 2 = 3,4-Me2C6H3; 1u: R = Me, Ar 1 = 3,4-(MeO)2C6H3, Ar 2 = Ph; 1v: R = Me, Ar 1 = Ph, Ar 2 = 4-ClC6H4; 1w: R = Me, Ar 1 = 4-ClC6H4, Ar 2 = 4-ClC6H4.

3. A method for preparing the o - hydroxydihydronaphthoate compound according to claim 1, reacting the triaryldivinyl ketone shown in formula [2] under the catalysis of the chiral ligand shown in formula [Pybox] and a rare - earth trifluoromethanesulfonate to obtain the highly optically active o - hydroxydihydronaphthoate compound shown in formula [1]: Wherein: R represents an alkyl group, cycloalkyl group, cycloalkylalkyl group having 1 to 6 carbon atoms; Ar 1 and Ar 2 represents a phenyl group, alkylphenyl group, alkoxyphenyl group, dialkylphenyl group, dialkoxyphenyl group, trialkylphenyl group, trialkoxyphenyl group having 6 to 12 carbon atoms, and phenyl group substituted with fluorine, chlorine, bromine, iodine, nitro group, cyano group, trifluoromethyl group, methanesulfonyl group; biphenyl group, furan group and thiophenyl group; Ar 1 and Ar 2 may be the same or different; RE is Ce, La, Tb, Sm, Pr, Eu, Gd, Ho, Er.

4. The preparation method of the o-hydroxy naphthalenedicarboxylate compound according to claim 3, characterized in that The rare - earth salt used is a rare - earth trifluoromethanesulfonate of Ce, La, Tb, Sm, Pr, Eu, Gd, Ho, Er.

5. The preparation method of the o-hydroxynaphthalenedicarboxylate compound according to claim 3, characterized in that The catalyst used is directly a complex formed by the chiral ligand shown in formula [Pybox] and a rare - earth trifluoromethanesulfonate of Ce, La, Tb, Sm, Pr, Eu, Gd, Ho, Er.

6. The preparation method of the o-hydroxydihydronaphthalene carboxylate compound according to claim 3, characterized in that The triaryldivinyl ketone shown in formula [2] reacts under the catalysis of the chiral ligand shown in formula [Pybox] and a rare - earth trifluoromethanesulfonate, and is stirred at - 40 °C to 80 °C to obtain the highly optically active o - hydroxydihydronaphthoate compound shown in formula [1].

7. The preparation method of the o-hydroxy naphthalenedicarboxylate compound according to claim 3, characterized in that The triaryldivinyl ketone shown in formula [2] reacts under the catalysis of a complex formed by the chiral ligand shown in formula [Pybox] and a rare - earth trifluoromethanesulfonate of Ce, La, Tb, Sm, Pr, Eu, Gd, Ho, Er, and is stirred at - 40 °C to 80 °C to obtain the highly optically active o - hydroxydihydronaphthoate compound shown in formula [1].

8. The preparation method of the o-hydroxynaphthoic acid ester compounds according to claim 3, characterized in that The solvent used is 1,2 - dichloroethane, chloroform, dichloromethane, chlorobenzene, tetrahydrofuran, benzene, toluene, xylene, trifluoromethylbenzene or a mixture thereof.

9. The o-hydroxy-dihydronaphthalene carboxylate compound represented by formula [1] as described in claim 1, characterized in that It can be used as a monomer for preparing polyester materials with high optical activity.

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