布朗斯特酸催化下硫代羧酸与(氮杂)邻亚甲基醌的共轭加成反应

doi:10.6023/cjoc202411004J

摘要/Abstract

报道了一种布朗斯特酸催化下硫代羧酸与原位生成的邻亚甲基醌和氮杂邻亚甲基醌之间的共轭加成反应. 该反应具有底物适用范围广、反应条件温和、操作简单和产率高的优点, 为在温和条件下高效构建具有结构多样性的硫酯类化合物提供了新的方法.

An efficient Brønsted acid catalyzed conjugate addition of thiocarboxylic acids to in situ-generated ortho-quinone methides (o-QMs) and aza-ortho-quinone methides (aza-o-QMs) has been reported. The reaction has the advantages of broad substrate scope, mild reaction conditions, easy operation and excellent yield. This study provides a new synthetic methodology for the efficient construction of structurally diverse thioesters under mild conditions.

Key words: ortho-quinone methides, aza-ortho-quinone methides, thiocarboxylic acids, conjugate addition

引用此文

薛秀, 杨惠儿, 黄泽深, 郎明, 刘文锋. 布朗斯特酸催化下硫代羧酸与(氮杂)邻亚甲基醌的共轭加成反应[J]. 有机化学, 2025, 45(8): 2968-2982.

Xiu Xue, Huier Yang, Zeshen Huang, Ming Lang, Wenfeng Liu. Brønsted Acid Catalyzed Conjugate Addition of Thiocarboxylic Acids to in situ-Generated (aza-)ortho-Quinone Methides[J]. Chinese Journal of Organic Chemistry, 2025, 45(8): 2968-2982.

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图/表 8

图式1. 背景及反应设计

Scheme 1. Background and reaction design

Entry	Cat.	Solvent	Yield^b/%	Entry	Cat.	Solvent	Yield^b/%
1	A	CH₂Cl₂	>99	9	A	CH₃CO₂Et	47
2	B	CH₂Cl₂	48	10	A	CH₃COCH₃	39
3	C	CH₂Cl₂	Trace	11	A	CH₃C₆H₅	88
4	D	CH₂Cl₂	99	12	A	ClC₆H₅	94
5	E	CH₂Cl₂	95	13	A		Trace
6	F	CH₂Cl₂	73	14	A		Trace
7	G	CH₂Cl₂	Trace	15	—	CH₂Cl₂	0
8	A	CH₃CN	54

表1. 反应条件的优化

Table 1. Optimization of reaction conditionsa

图式2. 邻羟基苄醇底物普适性研究

Scheme 2. Substrate scope of o-hydroxybenzyl alcohols

图式3. 硫代羧酸底物普适性研究

Scheme 3. Substrate scope of thiocarboxylic acids

图式4. 邻氨基苯甲醇与硫代羧酸的反应

Scheme 4. Reaction of o-aminobenzyl alcohols with thiocarboxylic acids

图式5. 反应的实用性

Scheme 5. Practicality of the reactions (a) Gram-scale synthesis of 3a and 6a; (b) synthetic transformation of compound 3a.

图式6. 对照实验

Scheme 6. Control experiment

图式7. 可能的反应机理

Scheme 7. Proposed mechanism of the reaction

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