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A kind of biaryl axis chiral alkyl sulfide and its synthesis method and application

A synthetic method and axial chiral technology, applied in the application field of asymmetric reactions as a chiral catalyst, can solve the problems of low synthesis method efficiency, expensive reagents, etc., and achieve mild reaction conditions, simple post-treatment, and total yield high rate effect

Active Publication Date: 2021-10-15
ZHEJIANG UNIV OF TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Solve the problem that the previous synthesis of biaryl axis chiral alkyl sulfides requires the use of expensive reagents or low efficiency of the synthesis method

Method used

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  • A kind of biaryl axis chiral alkyl sulfide and its synthesis method and application
  • A kind of biaryl axis chiral alkyl sulfide and its synthesis method and application
  • A kind of biaryl axis chiral alkyl sulfide and its synthesis method and application

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Experimental program
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Effect test

Embodiment 1

[0043]

[0044] Synthesis of Compound IIIa

[0045] Optically pure biaryl raw material Ia (91.4 mg, 0.2 mmol), methyl iodide (42.6 mg, 0.3 mmol), potassium hydroxide (22.4 mg, 0.4 mmol) were dissolved in 4 mL of ethanol, and the solution was stirred at room temperature for 3 h. . Concentrated, and subjected to silica gel column chromatography, eluting with petroleum ether / ethyl acetate = 80:1, and concentrated to obtain 67.3 mg of the product with a yield of 95%.

[0046] 1 H NMR (500MHz, CDCl 3 )δ=7.86–7.79(m, 1H), 7.33(t, J=7.8Hz, 1H), 7.29(dt, J=7.5, 1.0Hz, 1H), 7.16–7.08(m, 2H), 7.01(t , J=7.7Hz, 1H), 2.40(s, 3H), 2.06(s, 3H), 1.95(s, 3H) ppm. 13 C NMR (126MHz, CDCl 3 ) δ=143.2, 141.2, 138.4, 137.7, 136.9, 136.0, 130.0, 129.4, 128.3, 126.3, 121.8, 101.4, 21.2, 19.7, 15.4 ppm. The ee value was determined by HPLC using a chiral IC column (n-hexane: isopropyl Alcohol = 99.5: 0.5, 0.6 mL / min, 254 nm, 99% ee); t r =6.23min(S),t r =6.49min(R). The product structure ...

Embodiment 2

[0049] Synthesis of Compound IIIb

[0050] Optically pure biaryl starting material Ia (91.4 mg, 0.2 mmol), 2-iodopropane (51.0 mg, 0.3 mmol), potassium hydroxide (22.4 mg, 0.4 mmol) were dissolved in 4 mL of ethanol at room temperature The reaction was stirred for 3h. Concentrated, and subjected to silica gel column chromatography, eluting with petroleum ether / ethyl acetate=80:1, and concentrated to obtain 68.0 mg of the product with a yield of 89%.

[0051] 1 H NMR (500MHz, CDCl 3 )δ=7.80 (ddd, J=8.0, 1.2, 0.7Hz, 1H), 7.31–7.23 (m, 3H), 7.13–7.08 (m, 1H), 7.00 (t, J=7.7Hz, 1H), 3.51 (hept, J=6.7Hz, 1H), 2.04 (s, 3H), 1.93 (s, 3H), 1.31 (dd, J=11.5, 6.6Hz, 6H) ppm. 13 C NMR (126MHz, CDCl 3 )δ=143.6, 142.7, 138.1, 136.7, 136.4, 136.1, 129.8, 129.1, 128.0, 126.8, 124.8, 101.4, 35.4, 23.0, 22.9, 21.3, 19.9ppm.HRMS m / z(ESI): Calculated value C 17 H 19 INaS[M+Na] + 405.0144, found 405.0161.ee value was determined by HPLC using a chiral IC column (n-hexane:isopropanol=99.5:0...

Embodiment 3

[0054] Synthesis of Compound IIIc

[0055] Optically pure biaryl starting material Ia (91.4 mg, 0.2 mmol), bromocyclopentane (44.7 mg, 0.3 mmol), potassium hydroxide (22.4 mg, 0.4 mmol) were dissolved in 4 mL of ethanol at room temperature The reaction was stirred for 3h. Concentrated, and subjected to silica gel column chromatography, eluting with petroleum ether / ethyl acetate=100:1, and concentrated to obtain 68.5 mg of the product with a yield of 84%.

[0056] 1 H NMR (500MHz, CDCl 3 )δ=7.80(d,J=7.9Hz,1H),7.30–7.23(m,3H),7.08(ddd,J=7.2,1.6,0.8Hz,1H),7.00(t,J=7.7Hz,1H) ), 3.71–3.62 (m, 1H), 2.15–2.06 (m, 2H), 2.05 (s, 3H), 1.92 (s, 3H), 1.73 (ddq, J=12.8, 8.1, 2.6Hz, 2H), 1.67–1.51(m,4H)ppm. 13 C NMR (126MHz, CDCl 3 )δ=143.4,141.8,138.2,137.5,136.8,136.1,129.9,129.2,128.0,126.3,124.2,101.4,43.5,33.4,33.3,25.0,21.2,19.8ppm.HRMS m / z(ESI): Calculated value C 19 H 22 IS[M+H] + 409.0481, found 409.0493.ee value was determined by HPLC using a chiral IC column (n-hexane:i...

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Abstract

The invention provides a biaryl axis chiral alkyl sulfide (III) and its synthesis method and application. The present invention provides a nucleophilic substitution reaction between an optically pure biaryl axis chiral heterocyclic sulfide and a haloalkane, etc. , high-efficiency synthesis of biaryl axis chiral alkyl sulfur compounds, the reaction can be carried out under air, simple operation, mild reaction conditions, convenient post-treatment, easy to obtain raw materials, high overall yield, the obtained biaryl axis of the present invention The ee value of the chiral compound is up to 99%, and the yield can be as high as 99%;

Description

technical field [0001] The invention relates to a biaryl-axis chiral alkyl sulfide and a synthesis method thereof, as well as its application as a chiral catalyst in asymmetric reactions. Background technique [0002] Biaryl-like axial chiral compounds are widely found in natural products, bioactive molecules, chiral ligands, drug molecules and liquid crystal materials due to their special chemical structures (Angew.Chem.Int.Ed., 2005,44, 5384.; Chem. Rev., 2011, 111, 563.; Nat. Prod. Rep., 2015, 32, 1562.; Future. Med. Chem. 2018, 10, 409.). As chiral ligands, biaryl-like axial chiral compounds play an important role in a variety of asymmetric catalytic reaction systems. For example, the classical chiral ligands BINOL, BINAM, and BINAP all contain biaryl-axial chiral structural skeletons . Sulfur-containing compounds are a class of important structures that widely exist in fine chemicals, natural products, bioactive molecules, drug molecules, material molecules and chiral...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C323/09C07C319/14B01J31/02
CPCB01J31/0218C07C323/09
Inventor 张逢质朱凯王益
Owner ZHEJIANG UNIV OF TECH