open access

https://hdl.handle.net/2115/63311

Cp*Co-III Catalyzed Site-Selective C-H Activation of Unsymmetrical O-Acyl Oximes: Synthesis of Multisubstituted Isoquinolines from Terminal and Internal Alkynes

英語

transition-metal catalysis

2015-10-26

WILEY-VCH

Angewandte chemie-international edition

54(44)

12968-12972

The synthesis of isoquinolines by site-selective CH activation of O-acyl oximes with a Cp*Co-III catalyst is described. In the presence of this catalyst, the CH activation of various unsymmetrically substituted O-acyl oximes selectively occurred at the sterically less hindered site, and reactions with terminal as well as internal alkynes afforded the corresponding products in up to 98% yield. Whereas the reactions catalyzed by the Cp*Co-III system proceeded with high site selectivity (15:1 to 20:1), use of the corresponding Cp*Rh-III catalysts led to low selectivities and/or yields when unsymmetrical O-acyl oximes and terminal alkynes were used. Deuterium labeling studies indicate a clear difference in the site selectivity of the CH activation step under Cp*Co-III and Cp*Rh-III catalysis.

学術雑誌論文

Accepted Manuscript

This is the peer reviewed version of the following article: Sun, B., Yoshino, T., Kanai, M. and Matsunaga, S. (2015), Cp*CoIII Catalyzed Site-Selective C-H Activation of Unsymmetrical O-Acyl Oximes: Synthesis of Multisubstituted Isoquinolines from Terminal and Internal Alkynes. Angew. Chem. Int. Ed., 54: 12968-12972., which has been published in final form at http://dx.doi.org/10.1002/anie.201507744. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.

1433-7851