Enantioselective Copper-Catalyzed Mannich-Type Reaction of Cycic Ketimines and β,γ-Unsaturated N-Acylpyrazoles

doi:10.6023/cjoc202209034

Chinese Journal of Organic Chemistry ›› 2023, Vol. 43 ›› Issue (4): 1499-1509.DOI: 10.6023/cjoc202209034 Previous Articles Next Articles

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铜催化环酮亚胺与β,γ-不饱和N-酰基吡唑不对称Mannich-Type反应

刘洋^a^,^b, 黄翔^b^,^c, 王敏^a^,^b^,^*(), 廖建^a^,^b^,^c^,^*()

a 中国科学院成都生物研究所成都 610041
b 中国科学院大学北京 100049
c 中国科学院成都有机化学研究所成都 610041

收稿日期:2022-09-28 修回日期:2022-11-14 发布日期:2022-12-07
通讯作者: 王敏, 廖建
基金资助:
中国科学院青年创新促进会(2022375); 国家自然科学基金(21871251); 国家自然科学基金(22171258); 中国科学院生物资源(KFJ-BRP-008)

Enantioselective Copper-Catalyzed Mannich-Type Reaction of Cycic Ketimines and β,γ-Unsaturated N-Acylpyrazoles

Yang Liu^a^,^b, Xiang Huang^b^,^c, Min Wang^a^,^b(), Jian Liao^a^,^b^,^c()

a Chengdu Institute of Biology, Chinese Academy of Sciences, Chengdu 610041
b University of Chinese Academy of Sciences, Beijing 100049
c Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041

Received:2022-09-28 Revised:2022-11-14 Published:2022-12-07
Contact: Min Wang, Jian Liao
Supported by:
Youth Innovation Promotion Association of Chinese Academy of Sciences(2022375); National Natural Science Foundation of China(21871251); National Natural Science Foundation of China(22171258); Biological Resources Program, Chinese Academy of Sciences(KFJ-BRP-008)

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Abstract

Chiral benzosultams are an important category of bioactive compounds and functional organic molecules. Therefore, great efforts have been devoted for developing efficient methods for their preparation. A copper-catalyzed direct asymmetric Mannich-type reaction of cyclic N-sulfonyl α-iminoesters with β,γ-unsaturated N-acylpyrazoles was developed. Under mild conditions, γ-adducts were delivered in good yields with excellent regio- (γ/α>20/1), diastereoselectivities (dr>20/1) and high enantioselectivities (up to 93% ee). This method, with wide substrate-scopes and good functional group compatibility, provides potentiality for the synthesis of structurally diverse chiral benzosultam derivatives.

Key words: copper catalysis, chiral cyclic benzosulfonamide, asymmetric Mannich reaction, γ-adducts

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Yang Liu, Xiang Huang, Min Wang, Jian Liao. Enantioselective Copper-Catalyzed Mannich-Type Reaction of Cycic Ketimines and β,γ-Unsaturated N-Acylpyrazoles[J]. Chinese Journal of Organic Chemistry, 2023, 43(4): 1499-1509.

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Fig. & Tab. 6

Figure 1. Selected examples of important chiral benzosultams

Scheme 1. Asymmetric Mannich reactions of imines and β,γ-unsaturated carbonyl compounds

Entry	Ligand	Additive	Yield^b/%	ee^c/%
1	L1		60	4
2	L2		42	0
3	L3		59	0
4	L4		87	－12
5	L5		71	18
6	L6		56	8
7	L7		70	16
8	L8		60	30
9	L8	HCOOH	93	79
10	L8	AcOH	49	54
11	L8	TFA	41	34
12	L8	MeOH	36	30
13^d	L8	HCOOH	99 (94^e)	83
14^f	L8	HCOOCs	93	83

Table 1. Optimizations of the reaction conditions for synthesis of chiral benzosultams

Table 2. Enantioselective copper-catalyzed Mannich-type reaction for synthesis of chiral benzosultams

Scheme 2. Transformations of the product 3k

Figure 2. Proposed catalytic transition state model

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铜催化环酮亚胺与β,γ-不饱和N-酰基吡唑不对称Mannich-Type反应

Enantioselective Copper-Catalyzed Mannich-Type Reaction of Cycic Ketimines and β,γ-Unsaturated N-Acylpyrazoles

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