互利共生在有机化学中的应用: 锡氢烷的杂脱氢偶联与喹啉还原的相互促进

doi:10.1016/S1872-2067(23)64590-5

摘要/Abstract

摘要：

S, O, N, P与Sn原子组成的杂原子锡化合物(SSn, OSn, NSn和PSn)在有机合成和医药领域中具有广泛的应用. 目前, 构建杂原子锡化合物主要采用传统的复分解方法, 但这种方法反应条件苛刻且效率低. 其他构建杂原子锡化合物的方法, 如加成反应和自由基反应等, 也存在底物范围较窄的问题. 在锡烷杂脱氢偶联反应中, 锡烷上的负氢和杂原子上的正氢以氢气的方式逸出, 该过程需要较高的反应能量, 可能导致部分底物反应困难或效率低. 为了解决上述问题, 本课题组在前期工作中(Adv. Synth. Catal., 2021, 363, 5319-5329) 将互利共生的概念应用于有机合成, 采用B(C₆F₅)₃作为催化剂, 通过一锅法实现吲哚的C3位硅烷化或硼烷化以及喹啉的还原. 在这一过程中, 喹啉能够将副产物吲哚啉上的正氢和负氢通过氢转移的方式移除, 既促进了吲哚的官能化反应, 又实现了自身的还原.

在前期工作的基础上, 本文以B(C₆F₅)₃为催化剂, 在锡烷杂脱氢偶联反应中引入喹啉, 协助锡烷和杂原子上的负氢和正氢以氢转移的方式移除, 该反应同时会促进喹啉还原得到四氢喹啉. 在反应过程中, B(C₆F₅)₃催化喹啉的1,4-氢锡化反应生成少量1,4-N-锡化-二氢喹啉, 反应很快达到平衡. 同时游离的B(C₆F₅)₃与杂原子氢化合物(EH)底物组成中间体[ESnH]⁺[HB(C₆F₅)₃]^‒, 该中间体通过氢转移将1,4-N-锡化-二氢喹啉中间体转化为N-锡化-四氢喹啉进而加速喹啉的还原, 而1,4-N-锡化-二氢喹啉可以作为氢受体促进[ESnH]⁺[HB(C₆F₅)₃]^‒中间体转化生成ESn (E = S, O, N和P). N-锡化-四氢喹啉与EH发生复分解反应迅速生成另一分子ESn和四氢喹啉, 实现相互促进的过程. 该策略能够在温和条件下快速获得57种ESn产物和17种四氢喹啉产物. 在喹啉的辅助下, 含有较大位阻或强吸电子基团的酚类、部分烷基醇、苯胺、吲哚、烷基或芳基磷底物的产率明显提升. 利用该反应体系, 以较高的产率合成了两种药物结构的类似物. 根据一系列控制实验、反应监测、关键中间体捕获及合成实验和氘代控制实验结果, 提出了反应机理. 该互促反应由三部分组成, 分别为喹啉的1,4-氢锡化、正负氢转移以及复分解反应, 氢锡化和氢转移反应相互促进, 复分解反应同时促进氢锡化和氢转移, 进而实现整个反应的相互促进.

综上, 本工作高效合成了杂原子锡化合物以及四氢喹啉化合物, 并对反应机理进行了详尽的研究和阐述, 为有机锡化合物的构建和应用提供借鉴和参考.

关键词: 互利共生, 三(五氟)苯基硼, 杂脱氢偶联, 还原反应, 喹啉

Abstract:

Here we report a one-pot strategy to simultaneously achieve both the heterodehydrocoupling of hydrostannane and reduction of quinoline by using B(C₆F₅)₃ as catalyst under mild conditions. This method realizes the synthesis of heteroatom-tin complexes (NSn/OSn/PSn/SSn) by the same catalyst system. With the assistance of quinoline, the substrate scope was broadened and ESn yield was significantly enhanced. During the reaction, the generated heterodehydrocoupling intermediate [ESnH]⁺[HB(C₆F₅)₃]^- would accelerate the quinoline reduction by transforming 1,4-N-stannyl-dihydroquinoline intermediate into N-stannyl-tetrahydroquinoline whereas 1,4-N-stannyl-dihydroquinoline could serve as hydrogen acceptor to facilitate the conversion of [ESnH]⁺[HB(C₆F₅)₃]^- intermediate to produce ESn (E = N/O/P/S). The metathetical reaction of N-stannyl-tetrahydroquinoline and EH rapidly generates ESn and tetrahydroquinolines, thus mutually promoting the above process. The reaction mechanism is proposed on the basis of control experiments, capture and synthesis of key intermediates and deuterium experiments.

Key words: Mutualism, B(C₆F₅)₃, Heterodehydrocoupling, Reduction reaction, Quinoline

刘天伟, 何江华, 张越涛. 互利共生在有机化学中的应用: 锡氢烷的杂脱氢偶联与喹啉还原的相互促进[J]. 催化学报, 2024, 58: 129-137.

Tianwei Liu, Jianghua He, Yuetao Zhang. Mutualism in organic synthetic chemistry: Simultaneous heterodehydrocoupling of hydrostannane and reduction of quinoline[J]. Chinese Journal of Catalysis, 2024, 58: 129-137.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64590-5

https://www.cjcatal.com/CN/Y2024/V58/I3/129

图/表 9

Scheme 1. (a) Traditional ESn synthesis. (b) Frustrated Lewis Pair (FLP) catalyzed reduction of N-Heterocycles by H2. (c) Mutual promotion between borylation/silylation of indoles and reduction of quinolines (our previous work, ref. 39). (d) B(C6F5)3 catalyzed ESn (E = S, O, N, P) bond formation assisted by quinoline (this work).

Table 1 Scope for the B(C6F5)3 catalyzed dehydrocoupling of (nBu)3SnH and EH (E = S) a.

Table 2 Scope for the B(C6F5)3-catalyzed dehydrocoupling of (nBu)3SnH and EH (E = O/N/P).

Table 3 Scope of EH (E= S/O/N/P) for reaction with quinolone.

Table 4 Scope of quinolines for the mutual promotion reaction.

Entry	R	Yield (%)		Entry	R	Yield (%)
Entry	R	6g	13	Entry	R	6g	13
1	R = 2-Me	92	13b 92	10	R = 6-F	97	13k 97
2	R = 3-Me	83	13c 83	11	R = 6-Cl	96	13l 96
3	R = 4-Me	29	13d 0	12	R = 6-Br	95	13m 95
4	R = 5-Me	90	13e 90	13	R = 7-Br	97	13n 95
5	R = 6-Me	98	13f 98	14	R = 8-Br	96	13o 95
6	R = 6-OMe	92	13g 92	15	R = 6-Br, 7-F	95	13p 95
7	R = 7-Me	93	13h 93	16	R=6-Br, 5,7-F	89	13q 89
8	R = 8-Me	97	13i 97	17	R = 2-Ph	91	13r 91
9	R = 5-Br	97	13j 97

Scheme 2. Control experiments.

Fig. 1. Reaction process monitoring of the B(C6F5)3-catalyzed reaction of 2e with quinoline and (nBu)3SnH at RT.

Scheme 3. Possible mechanism for the quinoline assisted ESn bond formation catalyzed by B(C6F5)3.

Scheme 4. Deuterium-labelled experiments.

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