Research support from the Ministry of Education in Singapore (ARC12/07, no. T206B3225) and Nanyang Technological University (URC, RG53/07 and SEP, RG140/06) is gratefully acknowledged. We thank Prof. Daiqian Xie for helpful discussions, and Dr. Yongxin Li for the X-ray crystallographic analysis.
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Communication
Organocatalytic Asymmetric α-Aminoxylation/Aza-Michael Reactions for the Synthesis of Functionalized Tetrahydro-1,2-oxazines†
Article first published online: 8 OCT 2008
DOI: 10.1002/anie.200803731
Copyright © 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Issue
Angewandte Chemie International Edition
Volume 47, Issue 52, pages 10187–10191, December 15, 2008
Additional Information
How to Cite
Lu, M., Zhu, D., Lu, Y., Hou, Y., Tan, B. and Zhong, G. (2008), Organocatalytic Asymmetric α-Aminoxylation/Aza-Michael Reactions for the Synthesis of Functionalized Tetrahydro-1,2-oxazines. Angewandte Chemie International Edition, 47: 10187–10191. doi: 10.1002/anie.200803731
- †
Publication History
- Issue published online: 12 DEC 2008
- Article first published online: 8 OCT 2008
- Manuscript Received: 31 JUL 2008
Funded by
- Ministry of Education in Singapore. Grant Number: T206B3225
- Nanyang Technological University. Grant Numbers: RG53/07, RG140/06
Keywords:
- aminoxylation;
- asymmetric catalysis;
- cyclizations;
- domino reactions;
- organocatalysis
Graphical Abstract
Catalyst for THOught: The title reaction using acyclic nitroalkenals for the asymmetric installation of both C![[BOND]](http://onlinelibrarystatic.wiley.com/undisplayable_characters/00f8ff.gif)
O and CN bonds led to functionalized tetrahydro-1,2-oxazines (THOs) having up to three stereogenic centers; the products were isolated in up to 90 % yield with excellent enantioselectivity and complete diastereoselectivity (see scheme). DFT calculations reveal an unprecedented transition state containing a molecule of water, which assists in the CN bond-forming step by participating in two hydrogen bonds.