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

doi:10.6023/cjoc202209034

摘要/Abstract

手性苯并环状磺酰胺是一类重要的生物活性化合物和功能性有机分子, 发展其高效的不对称催化合成方法一直备受关注. 铜催化环状N-磺酰亚胺与β,γ-不饱和N-酰基吡唑的不对称Mannich-type反应是一类新合成策略. 在温和反应条件下, 该方法以良好的产率, 优异的选择性(区域选择性(γ/α>20/1)、非对映选择性(dr>20/1)、对映选择性(up to 93% ee)得到γ-加成产物手性苯并五元环状磺酰胺, 且底物范围较广, 官能团兼容性较好, 为结构多样的手性苯并环状磺酰胺及其衍生物合成提供新的合成途径.

关键词: 铜催化, 手性苯并环状磺酰胺, 不对称Mannich反应, γ-加成产物

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

引用此文

刘洋, 黄翔, 王敏, 廖建. 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[J]. 有机化学, 2023, 43(4): 1499-1509.

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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图/表 6

图1. 代表性手性苯并磺酰胺分子

Figure 1. Selected examples of important chiral benzosultams

图式1. 亚胺和β,γ-不饱和羰基化合物的不对称Mannich反应

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

表1. 手性苯并环状磺酰胺合成反应条件优化a

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

表2. 铜催化不对称Mannich-Type反应构建手性苯并五元环状磺酰胺a

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

图式2. 产物3k的转化

Scheme 2. Transformations of the product 3k

图2. 可能的催化过渡态模型

Figure 2. Proposed catalytic transition state model

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