These authors contributed equally to this work.
Copper-Catalyzed Cyclization/aza-Claisen Rearrangement Cascade Initiated by Ketenimine Formation: An Efficient Stereocontrolled Synthesis of α-Allyl Cyclic Amidines†
Article first published online: 2 JUL 2014
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Angewandte Chemie International Edition
Volume 53, Issue 35, pages 9284–9288, August 25, 2014
How to Cite
Xu, H.-D., Jia, Z.-H., Xu, K., Han, M., Jiang, S.-N., Cao, J., Wang, J.-C. and Shen, M.-H. (2014), Copper-Catalyzed Cyclization/aza-Claisen Rearrangement Cascade Initiated by Ketenimine Formation: An Efficient Stereocontrolled Synthesis of α-Allyl Cyclic Amidines. Angew. Chem. Int. Ed., 53: 9284–9288. doi: 10.1002/anie.201405331
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.
- Issue published online: 21 AUG 2014
- Article first published online: 2 JUL 2014
- Manuscript Received: 16 MAY 2014
- Natural Science Foundation of China. Grant Numbers: 21002032, 21272077
- Shanghai Pujiang Program. Grant Number: 11J1403100
- Priority Academic Program Development of Jiangsu High Education Institutions (PAPD)
- Natural Science Foundation of Jiangsu Province. Grant Number: SBK201321632
- allylic compounds;
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.