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铱/锌共催化的化学和对映选择性[2+2+2]环加成反应构建C─N轴手性吲哚和吡咯。

Ir/Zn-cocatalyzed chemo- and atroposelective [2+2+2] cycloaddition for construction of C─N axially chiral indoles and pyrroles.

作者信息

Yang Jian, Xie Zhong-Yang, Ye Yu-Jie, Ye Sheng-Bing, Wang Yi-Bo, Wang Wen-Tao, Qian Peng-Cheng, Song Ren-Jie, Sun Qing, Ye Long-Wu, Li Long

机构信息

College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, China.

Wenzhou Key Laboratory of Technology and Application of Environmental Functional Materials, Institute of New Materials and Industry Technology, Wenzhou University, Wenzhou 325000, China.

出版信息

Sci Adv. 2023 Dec 22;9(51):eadk1704. doi: 10.1126/sciadv.adk1704. Epub 2023 Dec 20.

DOI:10.1126/sciadv.adk1704
PMID:38117883
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10732529/
Abstract

Here, an Ir/Zn-cocatalyzed atroposelective [2+2+2] cycloaddition of 1,6-diynes and ynamines was developed, forging various functionalized C─N axially chiral indoles and pyrroles in generally good to excellent yields (up to 99%), excellent chemoselectivities, and high enantioselectivities (up to 98% enantiomeric excess) with wide substrate scope. This cocatalyzed strategy not only provided an alternative promising and reliable way for asymmetric alkyne [2+2+2] cyclotrimerization in an easy handle but also settled the issues of previous [Rh(COD)]BF-catalyzed system on the construction of C─N axial chirality such as complex operations, limited substrate scope, and low efficiency. In addition, control experiments and theoretical calculations disclosed that Zn(OTf) markedly reduced the barrier of migration insertion to significantly increase reaction efficiency, which was distinctly different from previous work on the Lewis acid for improving reaction yield through accelerating oxidative addition and reductive elimination.

摘要

在此，开发了一种铱/锌共催化的1,6-二炔与烯炔胺的对映选择性[2+2+2]环加成反应，可生成各种官能化的C─N轴手性吲哚和吡咯，产率普遍良好至优异（高达99%），具有出色的化学选择性和高对映选择性（对映体过量高达98%），底物范围广泛。这种共催化策略不仅为易于操作的不对称炔烃[2+2+2]环三聚反应提供了一种有前景且可靠的替代方法，还解决了先前[Rh(COD)]BF催化体系在构建C─N轴手性方面存在的问题，如操作复杂、底物范围有限和效率低下等。此外，对照实验和理论计算表明，Zn(OTf)显著降低了迁移插入的势垒，从而显著提高了反应效率，这与先前关于通过加速氧化加成和还原消除来提高反应产率的路易斯酸的研究明显不同。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/df78/10732529/7acacfd4f7f7/sciadv.adk1704-f7.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/df78/10732529/35ab444829b0/sciadv.adk1704-f1.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/df78/10732529/b5113beba78d/sciadv.adk1704-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/df78/10732529/f635c9580500/sciadv.adk1704-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/df78/10732529/2e80f4ec1d30/sciadv.adk1704-f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/df78/10732529/7acacfd4f7f7/sciadv.adk1704-f7.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/df78/10732529/35ab444829b0/sciadv.adk1704-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/df78/10732529/d4fb96389753/sciadv.adk1704-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/df78/10732529/bf36627ea381/sciadv.adk1704-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/df78/10732529/b5113beba78d/sciadv.adk1704-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/df78/10732529/f635c9580500/sciadv.adk1704-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/df78/10732529/2e80f4ec1d30/sciadv.adk1704-f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/df78/10732529/7acacfd4f7f7/sciadv.adk1704-f7.jpg

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