Copper-Catalyzed Cyclization/aza-Claisen Rearrangement Cascade Initiated by Ketenimine Formation: An Efficient Stereocontrolled Synthesis of α-Allyl Cyclic Amidines

An efficient and convenient synthesis of α‐allyl cyclic amidines has been achieved by applying a novel cascade reaction. Copper(I)‐mediated in situ N‐sulfonyl ketenimine formation from the reaction of a terminal alkyne with sulfonyl azide is followed by an intramolecular nucleophilic attack on the c...

Full description

Saved in:
Bibliographic Details
Published inAngewandte Chemie International Edition Vol. 53; no. 35; pp. 9284 - 9288
Main Authors Xu, Hua-Dong, Jia, Zhi-Hong, Xu, Ke, Han, Mei, Jiang, Sai-Nan, Cao, Jing, Wang, Jia-Cheng, Shen, Mei-Hua
Format Journal Article
LanguageEnglish
Published Weinheim WILEY-VCH Verlag 25.08.2014
WILEY‐VCH Verlag
Wiley
Subjects
Alkynes
allylic compounds
Bearing
Carbon
Cascades
Chairs
Chemistry
Chemistry, Multidisciplinary
copper
cyclization
Formations
heterocycles
Physical Sciences
rearrangements
Science & Technology
Synthesis
Terminals
KETENES
OXOKETENIMINE
AMIDE SYNTHESIS
1,3-SHIFTS
1ST-CENTURY
cyclization
ALKYNE
INTRAMOLECULAR 2+2 CYCLOADDITION
SULFONYL AZIDE
IMIDOYLKETENE
heterocycles
allylic compounds
rearrangements
CHEMISTRY
copper
Online AccessGet full text

Cover

More Information
Summary:An efficient and convenient synthesis of α‐allyl cyclic amidines has been achieved by applying a novel cascade reaction. Copper(I)‐mediated in situ N‐sulfonyl ketenimine formation from the reaction of a terminal alkyne with sulfonyl azide is followed by an intramolecular nucleophilic attack on the central carbon atom by an allylic tertiary amine, and then an aza‐Claisen rearrangement takes place through a chair transition state to furnish the titled amidines with complete stereocontrol. After a pattern: A convenient copper‐catalyzed method for cyclic amidine synthesis with high yield under mild reaction conditions has been established. By using this method, tertiary allyl enynes, with broad substitution patterns, can be converted stereoselectively into α‐allyl cyclic amidines bearing multiple functionalities for potential elaboration. DIPEA=diisopropylethylamine.
Bibliography:ark:/67375/WNG-8ZVNW5JQ-W
istex:EA355890CA40BA840C196A2A228F3BE0BBDBB5F3
ArticleID:ANIE201405331
This work was supported by the Natural Science Foundation of China (21002032 and 21272077), Shanghai Pujiang Program (11J1403100), Priority Academic Program Development of Jiangsu High Education Institutions (PAPD), and the Natural Science Foundation of Jiangsu Province (SBK201321632). We are grateful to Prof. Yang Yang at the Instrument Analysis Center of CCZU for his generous help with the NOSEY analysis.
Priority Academic Program Development of Jiangsu High Education Institutions (PAPD)
Shanghai Pujiang Program - No. 11J1403100
Natural Science Foundation of China - No. 21002032; No. 21272077
Natural Science Foundation of Jiangsu Province - No. SBK201321632
These authors contributed equally to this work.
ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201405331