基于“一石二鸟”策略的羧基无痕导向其邻位C—H键官能团化反应

doi:10.6023/cjoc202106024

摘要/Abstract

C—H键作为有机化合物的基本单元, 实现其直接的C—H键官能团化反应是简洁的合成方法. 羧酸广泛存在于自然界, 基于羧基的导向基团与离去基团双重角色所驱动的过渡金属催化羧酸邻位C—H键官能团化可控合成, 不仅规避了C—H键活化过程中导向基团的额外引入与移除, 也彰显了基于羧基“一石二鸟”策略的C—H键活化简洁性与脱羧绿色性. 因此, 基于“一石二鸟”策略的羧基无痕导向其邻位C—H键官能团化反应, 能为可控定向合成提供新的策略和方法, 在合成化学上具有显著意义. 根据参与反应的偶联底物类型, 分别介绍了基于“一石二鸟”策略的过渡金属催化羧酸邻位C—H键活化与含重键试剂、芳基化试剂及含杂原子试剂的反应, 并对相关的一些反应机理进行了探讨.

关键词: 羧酸, 无痕导向基团, C—H键活化, 脱羧, 官能团化

Since C—H bond is the basic unit of organic compounds, it’s considered to be a concise synthesis method to implement direct functionalization of C—H bond. As carboxylic acids are widely found in nature, carboxyl group can act as both directing group and leaving group to drive transition metal-catalyzed controllable transformation of ortho-C—H bond functionalization of carboxylic acid that not only avoids the extra introduction and removal of the directing group in the process of C—H bond activation, but also highlights the simplicity of C—H bond activation and green of decarboxylation with “one stone and two birds” strategy of the carboxyl group. Therefore, basing on the strategy of “two birds with one stone”, ortho-C—H bond functionalization of carboxylic acid using carboxyl as a traceless directing group can provide a new strategy and method for controllable and directional synthesis, which has considerable significance in synthetic chemistry. According to the types of coupling partners involved in the transformations, transition metal-catalyzed ortho-C—H bond activations of carboxylic acids with multiple-bond-containing reagents, arylating compounds and heteroatom-containing chemicals are reviewed respectively based on the strategy of “two birds with one stone”, and the relevant reaction mechanisms are discussed.

Key words: carboxylic acid, traceless directing group, C—H bond activation, decarboxylation, functionalization

引用此文

付拯江, 曹晰晗, 尹健, 苟振宇, 伊学政, 蔡琥. 基于“一石二鸟”策略的羧基无痕导向其邻位C—H键官能团化反应[J]. 有机化学, 2022, 42(1): 67-74.

Zhengjiang Fu, Xihan Cao, Jian Yin, Zhenyu Gou, Xuezheng Yi, Hu Cai. ortho-C—H Bond Functionalization of Carboxylic Acid Using Carboxyl as a Traceless Directing Group Based on the Strategy of “Two Birds with One Stone”[J]. Chinese Journal of Organic Chemistry, 2022, 42(1): 67-74.

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图/表 10

图式1. 涉及C—H键活化反应的不同类型导向基团

Scheme 1. Different types of directing groups involved in C—H bond activation transformations

图式2. Miura与Satoh课题组报道的Pd催化(杂)芳环羧酸与烯或炔的反应

Scheme 2. Pd-catalyzed reaction of (hetero)aromatic carboxylic acids with alkenes or alkynes reported by the group of Miura and Satoh

图式3. Nakamura课题组报道的Rh/Ag催化异噁唑-4-甲酸与烯或亚砜叶立德的反应

Scheme 3. Rh/Ag-catalyzed reaction of isoxazole-4-carboxylic acids with alkenes or sulfoxide ylides reported by the group of Nakamura

图式4. Hong课题组报道的Pd催化二芳基乙酸与丙烯酸酯的反应

Scheme 4. Pd-catalyzed reaction of diaryl acetic acids with acrylates reported by the group of Hong

图式5. Goossen课题组报道的羧酸与炔合成不同类型化合物的反应

Scheme 5. Synthesis of different types of compounds through the reactions between carboxylic acids and alkynes reported by the group of Goossen

图式6. Larrosa课题组报道的氟代芳烃与炔的接力反应

Scheme 6. Relay reaction between fluoroarenes and alkynes reported by the group of Larrosa

图式7. 石先莹与李朝军等报道的芳基羧酸与ArNCO的反应

Scheme 7. Reaction of aryl carboxylic acids with ArNCO reported by Shi and Li

图式8. Goossen课题组报道的肉桂酸钾与芳基卤化物反应及机理

Scheme 8. Reaction and mechanism of potassium cinnamates with aryl halides reported by the group of Goossen

图式9. Larrosa课题组报道的芳基羧酸或苯酚与芳基碘化物反应

Scheme 9. Reactions of aryl carboxylic acids or phenols with aryl iodides reported by the group of Larrosa

图式10. 张逢质及石先莹等报道的芳基羧酸与环二芳基碘鎓盐或芳基羧酸的反应

Scheme 10. Reactions of aryl carboxylic acids with cyclic diaryliodonium salts or arene carboxylic acids reported by Zhang and Shi

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