钯催化不对称[3＋4]环加成构建吲哚并环庚烷

doi:10.6023/cjoc202302017

摘要/Abstract

报道了一种通过钯催化的脱羧方法, 能够以较好的收率、中等至优异的对映选择性, 以及良好的非对映选择性高效地合成吲哚并环庚烷类化合物. 在该方法中, 乙烯基吲哚噁唑酮被钯催化剂活化脱羧形成两性离子中间体, 接着被缺电子双烯所捕获发生不对称[3＋4]环加成反应.

关键词: 脱羧, 吲哚并环庚烷, 不对称, 环加成

A Pd-catalyzed decarboxylation strategy for the efficient synthesis of cyclohepta[b]indoles in good yields with good to excellent enantioselectivities and moderate diastereoselectivities is reported. In this procedure, viny indoloxazolidones were activated by Pd catalyst to generate zwitterionic intermediates in situ, which were then trapped by the electro-deficient diene species via the asymmetric [3＋4] cycloaddition process.

Key words: decarboxylation, cyclohepta[b]indoles, asymmetric, cycloadditions

引用此文

王熠, 张键, 刘飏子, 罗晓燕, 邓卫平. 钯催化不对称[3＋4]环加成构建吲哚并环庚烷[J]. 有机化学, 2023, 43(8): 2864-2877.

Yi Wang, Jian Zhang, Yangzi Liu, Xiaoyan Luo, Weiping Deng. Palladium-Catalyzed Asymmetric [3＋4] Cycloadditions for the Construction of Cyclohepta[b]indoles[J]. Chinese Journal of Organic Chemistry, 2023, 43(8): 2864-2877.

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图/表 6

Scheme 1. Transition metal-catalyzed cycloadditions with participation of vinyl indoloxazolidones

Scheme 2. Pd-catalyzed asymmetric cycloadditions for the construction of cyclohepta[b]indole core

Entry ^a	Ligand	Solvent	Yield^b/%	dr^c	ee^d/%
1	L1	DCM	83	10.2∶1	23
2	L2	DCM	73	7.6∶1	68
3	L3	DCM	93	10.1∶1	31
4	L4	DCM	44	2.9∶1	12
5	L5	DCM	59	4.0∶1	75
6	L6	DCM	76	3.5∶1	81
7	L7	DCM	45	3.4∶1	88
8	L8	DCM	70	4.0∶1	87
9	L9	DCM	73	3.3∶1	89
10	L10	DCM	74	5.2∶1	95
11	L11	DCM	43	>20∶1	68
12	L12	DCM	83	>20∶1	67
13	L10	THF	36	2.8∶1	86
14	L10	PhMe	30	1.1∶1	56
15	L10	CHCl₃	76	5.1∶1	94
16	L10	DCE	36	2.9∶1	44

Table 1. Optimization of the reaction conditionsa

Scheme 3. Substrate scope of Pd-catalyzed asymmetric [3＋4] cycloadditions

Scheme 4. Scale-up experiment and transformations

Scheme 5. Proposed mechanism for Pd-catalyzed asymmetric [3＋4] cycloadditions

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