Axially chiral arylethynyl silane compound and preparation method thereof

An ethynyl silane and axial chirality technology, which is applied in the field of axial chiral arylethynyl silane compounds and their preparation, can solve the problems of complex substrates, high solvent melting points, and scarce sources of raw materials such as ligands, and achieves a simple catalytic system. , The effect of low production cost and easy industrialization promotion

Active Publication Date: 2021-02-05
HANGZHOU NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] The present invention aims at the disadvantages of the method for preparing axial chiral aryl olefins in the prior art, such as complex substrates, scarce sources of raw materials such as ligands, and high melting point of solvents, and provides a preparation method for axial chiral arylethynyl silane compounds. The method adopts The ligands and substrates are cheap and easy to obtain, and the reaction selectivity is excellent

Method used

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  • Axially chiral arylethynyl silane compound and preparation method thereof
  • Axially chiral arylethynyl silane compound and preparation method thereof
  • Axially chiral arylethynyl silane compound and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] (E)-3-Methyl-2-(2-((triisopropylsilyl)ethynyl)naphthalene-1-yl)cyclohex-2-en-1-one-O-methyloxime

[0034]

[0035] To a 25 mL reaction tube was added 3-methyl-2-naphthylcyclohex-2-en-1-one-O-methyloxime (0.13 g, 0.2 mmol), (2-bromoethynyl)triisopropyl Silane (0.16g, 0.6mmol), palladium acetate (0.005g, 10mol%), N-acetyl-L-alanine (0.0053g, 20mol%), silver carbonate (0.165g, 0.6mmol), then add methanol ( 2mL). The reaction tube was moved to a 40°C oil bath for 48 hours. The mixture was purified by flash column chromatography to obtain a yellow liquid (82 mg, 0.184 mmol), with a yield of 92%.

[0036] H NMR spectrum such as figure 1 as shown, 1 H NMR (400MHz, CDCl 3 )δ7.82-7.77(m,1H),7.68(dd,J=12.8, 4.9Hz,2H),7.56(d,J=8.4Hz,1H),7.43(m,2H),3.52(s,3H ),2.88-2.75(m,1H),2.59(m,1H),2.34(m,2H),1.95(m,2H),1.44(s,3H),1.11(d,J=2.1Hz,18H) .Carbon spectrum such as figure 2 as shown, 13 C NMR (100MHz, CDCl 3 )δ155.78(s),143.66(s),140.31(s),133.01(s),132.15(s),129.28(s), 1...

Embodiment 2

[0038] (E)-3-Methyl-2-(4-methyl-2-((triisopropylsilyl)ethynyl)naphthalene-1-yl)cyclohex-2-en-1-one-O- Methyl oxime

[0039]

[0040] To a 25 mL reaction tube was added 3-methyl-2-naphthylmethyl-2-cyclohexen-1-one-O-methyloxime (0.056 g, 0.2 mmol), (2-bromoethynyl)triisopropyl Silane (0.16g, 0.6mmol), palladium chloride (0.0018g, 5mol%), Boc-D-valine (0.0043g, 10mol%), silver trifluoromethanesulfonate (0.102g, 0.4mmol), Additional methanol (1 mL) was added. The reaction tube was moved to a 50°C oil bath for 40 hours. The mixture was purified by flash column chromatography to obtain white liquid (36.8 mg, 0.08 mmol), yield 40%.

[0041] 1 H NMR (400MHz, CDCl 3 )δ7.95(d,J=8.0Hz,1H),7.74-7.65(m,1H),7.51-7.37(m,3H),3.53(s,3H),2.82(m,1H),2.67(s ,3H),2.63-2.50(m,1H),2.34(m,2H),1.95(m,2H),1.45(s,3H),1.12(d,J=2.5Hz,18H). 13 C NMR (100MHz, CDCl 3 )δ155.89(s),143.69(s),138.62(s),132.85(s),132.40(s),132.24(s),129.72(s),128.75(s),126.92(s),125.99( s), 125.88(s), 124.24(s), 120....

Embodiment 3

[0043] (E)-2'-methoxy-6-methyl-6'((triisopropylsilyl)ethynyl)-4,5-dihydro-[1,1'-biphenyl]-2( 3H)-O-methyloxime

[0044]

[0045] To a 25 mL reaction tube was added 3-methyl-2-(2-methoxyphenyl)cyclohex-2-en-1-one-O-methyloxime (0.049 g, 0.2 mmol), (2-bromo Ethynyl) triisopropylsilane (0.16g, 0.4mmol), palladium tetraacetonitrile tetrafluoroborate (0.009g, 10mol%), Boc-L-isoleucine (0.0093g, 20mol%), silver carbonate (0.11 g, 0.4 mmol), and tetrahydrofuran (2 mL) was added. The reaction tube was moved to a 60°C oil bath for 36 hours. The mixture was purified by flash column chromatography to obtain white liquid (32.4 mg, 0.076 mmol), yield 38%.

[0046] 1 H NMR (400MHz, CDCl 3 )δ7.16(m,2H),6.87(dd,J=7.9,1.3Hz,1H),3.74(s,3H),3.66(s,3H),2.68-2.52(m,2H),2.33-2.16 (m,2H),1.89-1.77(m,2H),1.56(s,3H),1.08(d,J=2.7Hz,18H). 13 C NMR (100MHz, CDCl 3 )δ157.18(s),155.63(s),142.54(s),130.81(s),127.50(s),126.75(s),125.25(s),125.03(s),111.61(s),106.51( s), 91.41(s), 61.48(s), 56.32(...

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Abstract

The invention relates to the technical field of organic synthesis, and discloses an axially chiral arylethynyl silane compound and a preparation method thereof, the structural formula of the axially chiral arylethynyl silane compound is shown in the formula (1), the preparation method is as follows: a complex formed by palladium salt and ligand is used as a catalyst precursor, by taking 2-aryl cyclohexene-1-ketoxime and 2-bromoethynyl silane as reactants, asymmetric alkynylation is carried out on a carbon-hydrogen bond in the reactants in a reaction medium in the presence of an oxidizing agentto obtain the axially chiral arylethynyl silane compound. The method has good adaptability to aryl and alkynyl silane containing substituent groups with different properties, a series of axial chiralaryl ethynyl silane compounds can be obtained with medium to good yield and enantioselectivity, and silicon substituent groups in the compounds are easy to convert in a series, and the derivatives can be used as chiral ligands and catalysts in asymmetric catalytic reactions.

Description

technical field [0001] The invention relates to the technical field of organic synthesis, in particular to an axial chiral arylethynyl silane compound and a preparation method thereof. Background technique [0002] Axial chiral compounds widely exist in biologically active and pharmaceutical molecules, and are also widely used as chiral ligands and catalysts in asymmetric catalytic reactions. Compared with the more researched biaryl (hetero) ring-type axial chiral compounds, the research on aryl olefin compounds with a chiral axis between the aromatic ring and the olefin is relatively lagging behind in both synthesis and application. The main reason is that these compounds have low rotational energy barriers, are easy to racemize and are difficult to control the stereoselectivity of the reaction. The preparation of axial chiral aryl olefins was obtained by chemical resolution in the early days, and the synthesis of such compounds by asymmetric catalytic reactions has not be...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F7/08C07C251/44C07C249/12C07D249/06B01J31/22C07C209/00C07C211/45
CPCC07F7/081C07F7/083C07C251/44C07C249/12C07D249/06B01J31/2217C07C209/00C07B2200/09C07C2601/16B01J2531/16B01J2531/0241B01J2231/341C07C211/48Y02P20/55
Inventor 崔玉明徐利文李钊
Owner HANGZHOU NORMAL UNIVERSITY
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