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Dual-chiral-center cyclopropyl silane compound and preparation and application methods thereof

A technology of cyclopropylsilane and compound, which is applied in the field of chiral center cyclopropylsilane compound and its preparation, can solve the problems of limiting structure diversification and the like, and achieves strong substrate universality, mild reaction conditions and product yield and the effect of high enantioselectivity

Active Publication Date: 2019-10-11
HANGZHOU NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, such methods are very limited. For each cyclopropane, different alkene or carbene precursors are required, which greatly limits the structural diversification.

Method used

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  • Dual-chiral-center cyclopropyl silane compound and preparation and application methods thereof
  • Dual-chiral-center cyclopropyl silane compound and preparation and application methods thereof
  • Dual-chiral-center cyclopropyl silane compound and preparation and application methods thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0045] Under nitrogen atmosphere, add phosphine ligand L2:(R)-DTBM-SegPhos (8.5mg, 0.0072mmol) to Schlenk reaction tube, metal catalyst [Rh(cod) 2 ] BF 4 (2.5mg, 0.006mmol) and additive tetrakis(3,5-bis(trifluoromethyl)phenyl)sodium borate (5.3mg, 0.006mmol), then add 2.0mL n-hexane solvent, and pre-stir at 30°C for 20min Finally, add cyclopropene compound 1a (0.20mmol), stir for 15min, then add diphenylsilane (0.26mmol), continue to stir and react at 30°C for 20h, after the reaction is monitored by TLC, filter, extract, concentrate the filtrate, and pass through silica gel Purified by column chromatography, 50 mg of product 1c was obtained as a light yellow oily liquid with a yield of 70%, 92% ee, 93:7dr.

[0046]

[0047] The physicochemical index of this product: 1 H NMR (400MHz, CDCl 3 )δ7.64–7.57(m,2H),7.53(dd,J=7.1,2.0Hz,2H),7.28(dd,J=6.5,2.6Hz,4H),7.27–7.23(m,4H),7.19 (t,J=7.3Hz,2H),7.17–7.10(m,1H),4.90(d,J=4.4Hz,1H),3.22(s,3H),1.76(dd,J=8.6,3.4Hz, 1H), 1.56(dd,...

Embodiment 2

[0049] Under nitrogen atmosphere, add phosphine ligand L2:(R)-DTBM-SegPhos (8.5mg, 0.0072mmol) to Schlenk reaction tube, metal catalyst [Rh(cod) 2 ] BF 4 (2.5mg, 0.006mmol) and additive tetrakis(3,5-bis(trifluoromethyl)phenyl)sodium borate (5.3mg, 0.006mmol), then add 2.0mL n-hexane solvent, and pre-stir at 30°C for 40min Finally, add cyclopropene compound 1a (0.20mmol), stir for 15min, then add diphenylsilane (0.26mmol), continue to stir and react at 30°C for 20h, after the reaction is monitored by TLC, filter, extract, concentrate the filtrate, and pass through silica gel Purified by column chromatography, 60 mg of product 1c was obtained as light yellow oily liquid with a yield of 84%, 98% ee, 97:3dr.

[0050]

[0051] The physicochemical index of this product: 1 H NMR (400MHz, CDCl 3 )δ7.64–7.57(m,2H),7.53(dd,J=7.1,2.0Hz,2H),7.28(dd,J=6.5,2.6Hz,4H),7.27–7.23(m,4H),7.19 (t,J=7.3Hz,2H),7.17–7.10(m,1H),4.90(d,J=4.4Hz,1H),3.22(s,3H),1.76(dd,J=8.6,3.4Hz, 1H), 1.56(dd, J...

Embodiment 3

[0053] Under nitrogen atmosphere, add phosphine ligand L2:(R)-DTBM-SegPhos (8.5mg, 0.0072mmol) to Schlenk reaction tube, metal catalyst [Rh(cod) 2 ] BF 4 (2.5mg, 0.006mmol) and additive tetrakis(3,5-bis(trifluoromethyl)phenyl)sodium borate (5.3mg, 0.006mmol), then add 2.0mL n-hexane solvent, and pre-stir at 30°C for 60min Finally, add cyclopropene compound 1a (0.20mmol), stir for 15min, then add diphenylsilane (0.26mmol), continue to stir and react at 30°C for 20h, after the reaction is monitored by TLC, filter, extract, concentrate the filtrate, and pass through silica gel Purified by column chromatography, 50 mg of product 1c was obtained as a light yellow oily liquid with a yield of 70%, 90% ee, 90:10dr.

[0054]

[0055] The physicochemical index of this product: 1 H NMR (400MHz, CDCl 3 )δ7.64–7.57(m,2H),7.53(dd,J=7.1,2.0Hz,2H),7.28(dd,J=6.5,2.6Hz,4H),7.27–7.23(m,4H),7.19 (t,J=7.3Hz,2H),7.17–7.10(m,1H),4.90(d,J=4.4Hz,1H),3.22(s,3H),1.76(dd,J=8.6,3.4Hz, 1H), 1.56(dd...

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Abstract

The invention relates to the field of chiral organosilane and particularly discloses a dual-chiral-center cyclopropyl silane compound shown as the formula (I) and a preparation method thereof. The preparation method comprises subjecting cyclopropane shown as the formula (II) and diphenylsilane to asymmetric hydrogenation and salinization reaction to effectively synthesize the dual-chiral-center cyclopropyl silane compound high in yield and enantioselectivity. Compared with traditional reactions such as [2+1] cycloaddition and 1, 3-cyclization propylamino substitution, the preparation method ofthe dual-chiral-center cyclopropyl silane compound is more direct and more effective for synthesizing naphthene compounds and can help obtain multiple cyclopropyl silane compounds with different substituent groups which cannot be prepared through traditional methods, thereby being widely applicable to the field of material chemistry and medicinal chemistry.

Description

technical field [0001] The invention relates to the field of chiral organosilanes, in particular to a bichiral central cyclopropylsilane compound and its preparation method and application. Background technique [0002] Chiral organosilanes are gradually playing an important role in siliceous substitution in organic synthesis, materials science and medicinal chemistry, among which chiral silicon-containing organic compounds are very useful synthetic blocks in organic chemistry; silane-substituted compounds are due to their Low toxicity and favorable metabolic characteristics have attracted increasing attention in medicinal chemistry; chiral catalysts containing silicon atoms are also widely used in asymmetric organocatalysis. Silicon-based chiral compounds are important components for selective carbon-carbon bond formation, and the asymmetric hydrosilylation of alkenes provides a direct route to construct chiral organosilanes. [0003] 3,3-Disubstituted cyclopropylsilanes a...

Claims

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Application Information

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IPC IPC(8): C07F7/08C07F7/12C07D401/04C07C235/82C07C61/37C07C57/50
CPCC07F7/0896C07F7/122C07D401/04C07C235/82C07C61/37C07C57/50C07C2601/02C07C2602/10C07C2602/24C07B2200/07
Inventor 徐利文赵志远杨雪敏郭彬徐征曹建尹官武郑战江叶飞杨科芳崔玉明
Owner HANGZHOU NORMAL UNIVERSITY
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