Lewis acid-catalyzed domino generation/[2,3]-sigmatropic rearrangement of ammonium ylides to access chiral azabicycles

doi:10.1126/sciadv.abd5290

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	Lewis acid-catalyzed domino generation/[2,3]-sigmatropic rearrangement of ammonium ylides to access chiral azabicycles
	Xi,Song ; Dong,Jiawei ; Chen,Haohua ; Dong,Qiuyan ; Yang,Jiao ; Tan,Qiuyuan ; Zhang,Changhui ; Lan,Yu ; Zhang,Min
	2021
发表期刊	SCIENCE ADVANCES
ISSN	2375-2548
卷号	7 期号:5 页码:eabd5290
摘要	[2,3]-Sigmatropic rearrangement of ammonium ylides represents a fundamental reaction for stereoselective synthesis of nitrogenous compounds. However, its applicability is limited by the scarcity of efficient, catalytic, and mild methods for generating ammonium ylides. Here, we report silver-catalyzed domino generation/[2,3]-sigmatropic rearrangement of ammonium ylides, furnishing chiral azabicycles with bridgehead quaternary stereogenic centers in high enantiomeric purity (up to 99% ee). A combination of density functional theory calculations and experimental studies revealed that residual water in the reaction system is crucial for the mild reaction conditions by functioning as a proton shuttle to assist carbon-silver bond protonation and C2-H deprotonation to generate the ammonium ylide. This reaction has a broad application scope. Besides the diverse substituents, N-fused azabicycles of various ring sizes are also easily accessed. In addition to silver salts, this strategy has also been successfully implemented by using a stoichiometric amount of nonmetallic I-2.
DOI	10.1126/sciadv.abd5290
WOS记录号	WOS:000614004600022
引用统计
文献类型	期刊论文
条目标识符	http://ir.kib.ac.cn/handle/151853/73070
专题	中国科学院昆明植物研究所
作者单位	1.Chongqing Univ, Sch Pharmaceut Sci, Chongqing Key Lab Nat Prod Synth & Drug Res, Chongqing, Peoples R China 2.Chongqing Univ, Sch Chem & Chem Engn, Chongqing Key Lab Theoret & Computat Chem, Chongqing, Peoples R China 3.Zhengzhou Univ, Coll Chem, Green Catalysis Ctr, Zhengzhou, Peoples R China 4.Chinese Acad Sci, Kunming Inst Bot, State Key Lab Phytochem & Plant Resources West Ch, Kunming, Yunnan, Peoples R China
推荐引用方式 GB/T 7714	Xi,Song,Dong,Jiawei,Chen,Haohua,et al. Lewis acid-catalyzed domino generation/[2,3]-sigmatropic rearrangement of ammonium ylides to access chiral azabicycles[J]. SCIENCE ADVANCES,2021,7(5):eabd5290.
APA	Xi,Song.,Dong,Jiawei.,Chen,Haohua.,Dong,Qiuyan.,Yang,Jiao.,...&Zhang,Min.(2021).Lewis acid-catalyzed domino generation/[2,3]-sigmatropic rearrangement of ammonium ylides to access chiral azabicycles.SCIENCE ADVANCES,7(5),eabd5290.
MLA	Xi,Song,et al."Lewis acid-catalyzed domino generation/[2,3]-sigmatropic rearrangement of ammonium ylides to access chiral azabicycles".SCIENCE ADVANCES 7.5(2021):eabd5290.