中国科学(化学)2024,Vol.54Issue(7) :1099-1106.DOI:10.1360/SSC-2024-0012

纯水介质中银催化α,β-不饱和酮碳碳双键的选择性还原

Silver-catalyzed selectively reduction of the C=C bond of an α,β-unsaturated ketones in water

焦红梅 周慧 鲁星 高媛媛 侯雪艳 张玉琦 韩波
中国科学(化学)2024,Vol.54Issue(7) :1099-1106.DOI:10.1360/SSC-2024-0012

纯水介质中银催化α,β-不饱和酮碳碳双键的选择性还原

Silver-catalyzed selectively reduction of the C=C bond of an α,β-unsaturated ketones in water

焦红梅 1周慧 1鲁星 1高媛媛 1侯雪艳 1张玉琦 1韩波1
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作者信息

  • 1. 延安大学化学化工学院,陕西省化学反应工程重点实验室,新能源新功能材料重点实验室,延安 716000
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摘要

选择性还原α,β-不饱和酮中C=C键是有机化学中极具潜力且最有挑战性的官能团转化之一.本文以空气中稳定且极少量的N-杂环卡宾银配合物为催化剂、苯硅烷为还原剂,在水相且温和条件下,以较高的收率实现了α,β-不饱和酮化合物中双键的选择性还原,该体系可以兼容氟、氯、溴、三氟甲基、氨甲基、氰基及酯基等官能团,具有工业应用的潜质,TON值高达11250.该方法可用于药物分子的合成,后处理操作简单,避免了氢气及高压釜设备,为酮类的制备提供了新的思路和方法.初步机理研究表明,原位生成的银氢中间体为活性物种,随后对双键的加成是实现转化的关键,后经水解得到双键还原产物.

Abstract

The selective reduction of C=C bond in α,β-unsaturated ketones is one of the highly potent and challenging functional group transformations in organic chemistry.Therefore,the investigation of a simple and efficient new reductive system for the chemoselective reduction of α,β-unsaturated ketones is highly desirable.Herein,we presented a method for the homogeneous hydrogenation of C=C bond in the α,β-unsaturated carbonyl compound to produce ketone using low catalyst loading and air-stable silver N-heterocyclic carbene complexes as the catalyst and PhSiH3 as the source of hydrogen.A wide range of α,β-unsaturated ketones,featuring diverse functional groups,were selectively transformed into their corresponding ketones with moderate yields.This process can be readily scaled up and exhibits compatibility with various sensitive functional groups,including fluorine,chlorine,bromine,trifluoromethyl,aminomethyl,cyano and ester,with broad scope and particularly high turnover numbers(up to 11250).Notably,this catalytic methodology finds application in the synthesis of essential drug compounds.Meanwhile,the post-processing operation is simple and does not require hydrogen or autoclave equipment.Mechanistic investigations suggest that the in-situ-generated Ag-H species may serve as active intermediates.Intermediate is produced by the coordination of the C=C to AgH species,which is succeeded by the production of intermediate via the insertion of the C=C bonds into the Ag-H bond.The final product was obtained by hydrolysis intermediate in the presence of H2O.

关键词

α,β-不饱酮/选择性/还原//N-杂环卡宾银配合物

Key words

α,β-unsaturated ketones/selectivity/reduction/water/silver N-heterocyclic carbene complexes

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基金项目

国家自然科学基金(22061041)

陕西省重点研发计划(2023-YBGY-430)

陕西省重点研发计划(2022GY-412)

榆林市产学研计划(CXY-2022-185)

延安大学大学生创新创业训练计划(D2022077)

出版年

2024
中国科学(化学)
中国科学院

中国科学(化学)

CSTPCD北大核心
影响因子:0.685
ISSN:1674-7224
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