MgCl2-Catalyzed Chemoselective Reduction of Aldehydes, Ketones and Imines

doi:10.6023/cjoc202208042

Chinese Journal of Organic Chemistry ›› 2023, Vol. 43 ›› Issue (4): 1462-1471.DOI: 10.6023/cjoc202208042 Previous Articles Next Articles

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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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Abstract

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

Cite this article

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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Fig. & Tab. 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

Table 1. Optimization of the reaction conditions

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

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

。。。。。

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

Scheme 1. Gram-scale reduction of 1a

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

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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