氯化镁催化醛、酮及亚胺的化学选择性还原

doi:10.6023/cjoc202208042

有机化学 ›› 2023, Vol. 43 ›› Issue (4): 1462-1471.DOI: 10.6023/cjoc202208042 上一篇下一篇

研究论文

氯化镁催化醛、酮及亚胺的化学选择性还原

张苗苗, 陈荣, 焦红梅, 马豪杰, 韩波^*(), 张玉琦, 王记江

延安大学化学与化工学院新能源新功能材料重点实验室陕西省化学反应工程重点实验室陕西延安 716000

收稿日期:2022-08-30 修回日期:2022-10-18 发布日期:2022-12-07
通讯作者: 韩波
作者简介:
^†共同第一作者.
基金资助:
国家自然科学基金(22061041); 陕西省科技资源开放共享平台(2021PT-004); 延安大学博士科研启动经费(YDBK2019-60); 延安大学科研项目(YDY2020-61); 陕西省大学生创新创业训练计划(S202210719055)

MgCl₂-Catalyzed Chemoselective Reduction of Aldehydes, Ketones and Imines

Miaomiao Zhang, Rong Chen, Hongmei Jiao, Haojie Ma, Bo Han(), Yuqi Zhang, Jijiang Wang

Laboratory of New Energy ＆ New Function Materials, Shaanxi Key Laboratory of Chemical and Reaction Engineering, College of Chemistry and Chemical Engineering, Yan'an University, Yan'an, Shaanxi 716000

Received:2022-08-30 Revised:2022-10-18 Published:2022-12-07
Contact: Bo Han
About author:
^†These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22061041); Open Sharing Platform for Scientific and Technological Resources of Shaanxi Province(2021PT-004); Doctoral Research Foundation of Yan'an University(YDBK2019-60); Research Program of Yan'an University(YDY2020-61); Shaanxi Province Training Program of Innovation and Entrepreneurship for Undergraduates(S202210719055)

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摘要/Abstract

发展了一种操作简便、廉价实用的镁催化体系, 用于醛、酮及α,β-不饱和醛/酮的选择性还原, 制备了一系列醇类化合物. 以温和的HBpin为还原剂, 在没有酸或碱作为水解试剂的前提下, 高选择性地还原羰基, 体系中没有检测到硼酸酯副产物. 对碘、溴、氯、氟、硝基、三氟甲基、氨甲基、炔基和酰胺等官能团具有良好的兼容性, 在温和的条件下, MgCl₂/HBpin催化体系不仅对羰基具有较高的催化活性, 对亚胺类底物具有高效的催化效果.

关键词: 碱土金属, 镁, 羰基, 亚胺, 还原

An operationally convenient Mg-catalyzed synthesis of alcohols by the reduction of aldehydes, ketones and α,β-unsaturated aldehydes/ketones is reported. It is a rare example of using mild and sustainable HBpin as a reductant for catalytic reduction of carbonyl compounds in the absence of acid or base as hydrolysis reagent. The reaction is up-scalable, and proceeds in high selectivity without the formation of boronate ester by-products, and tolerates sensitive functionalities such as iodine, bromide, chloride, fluoride, nitro, trifluoromethyl, aminomethyl, alkynyl, and amide. The MgCl₂/HBpin combination has been also proved to be chemoselective for the C=N reduction of imine analogs.

Key words: alkaline-earth metals, magnesium, carbonyl, imine, reduction

引用此文

张苗苗, 陈荣, 焦红梅, 马豪杰, 韩波, 张玉琦, 王记江. 氯化镁催化醛、酮及亚胺的化学选择性还原[J]. 有机化学, 2023, 43(4): 1462-1471.

Miaomiao Zhang, Rong Chen, Hongmei Jiao, Haojie Ma, Bo Han, Yuqi Zhang, Jijiang Wang. MgCl₂-Catalyzed Chemoselective Reduction of Aldehydes, Ketones and Imines[J]. Chinese Journal of Organic Chemistry, 2023, 43(4): 1462-1471.

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图/表 7

Entry	Catalyst (mol%)	Solvent	Temp./℃	Time/h	Yield/%
1	Mg (100)	THF	45	24	92
2	MgSO₄ (100)	THF	45	24	52
3	MgCl₂ (50)	THF	45	24	93
4^b	MgCl₂ (50)	THF	45	24	Nd^c
5	MgCl₂ (10)	THF	45	24	93
6	MgCl₂ (5)	THF	45	24	95
7	MgCl₂ (1)	THF	45	24	93
8	MgCl₂ (1)	THF	r.t.	1	87
9	MgCl₂ (1)	Toluene	r.t.	1	87
10	MgCl₂ (1)	Dioxane	r.t.	1	53
11	MgCl₂ (1)	EtOH	r.t.	1	92 (90)^d
12	MgCl₂ (1)	CH₃CN	r.t.	1	69
13	MgCl₂ (1)	CH₂Cl₂	r.t.	1	Nd
14	MgCl₂ (1)	EtOAc	r.t.	1	78
15	MgCl₂ (1)	EtOH	r.t.	1	76^e
16	No	EtOH	r.t.	1	0

表1. 反应条件优化a

Table 1. Optimization of the reaction conditions

表2. 镁催化醛的还原的底物拓展a

Table 2. Scope for the Mg-catalyzed reduction of aldehydes

表3. 镁催化酮及不饱和醛酮的还原的底物拓展a

Table 3. Scope for the Mg-catalyzed reduction of ketones and α,β-unsaturated aldehyde/ketones

。。。。。

表4. 镁催化亚胺的还原的底物拓展a

Table 4. Substrate scope of Mg-catalyzed reduction of imines

图式1. 还原底物1a的克级反应

Scheme 1. Gram-scale reduction of 1a

图1. 镁催化底物1a还原的反应动力学研究

Figure 1. Kinetic profile for Mg-catalyzed reduction of 1a (a) Reaction profiles of Mg-catalyzed reduction of 1a; (b) initial reaction rate against the concentration of 1a; (c) initial reaction rate against the concentration of catalyst of MgCl2; (d) initial reaction rate against the HBpin

图式2. 镁催化醛, 酮及不饱和醛酮还原的可能机理

Scheme 2. Proposed mechanism for the Mg-catalyzed reduction of aldehydes, ketones and α,β-unsaturated aldehydes/ketones

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氯化镁催化醛、酮及亚胺的化学选择性还原

MgCl₂-Catalyzed Chemoselective Reduction of Aldehydes, Ketones and Imines

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氯化镁催化醛、酮及亚胺的化学选择性还原

MgCl2-Catalyzed Chemoselective Reduction of Aldehydes, Ketones and Imines

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MgCl₂-Catalyzed Chemoselective Reduction of Aldehydes, Ketones and Imines