Issue 9, 2011

Effects of geminal methyl groups on the tunnelling rates in the ring opening of cyclopropylcarbinyl radical at cryogenic temperature

Abstract

CVT + SCT calculations on the rate of tunnelling at 20 K in the ring opening of cyclopropylcarbinyl radical, substituted with geminal methyl groups at a ring carbon (1b), have been performed. The calculations predict that, contrary to expectations based on the effect of mass on the rate of tunnelling, the geminal methyl substituents in 1b should make the rate of ring opening to 1,1-dimethyl-3-butenyl radical (2b) 104 times faster than the rate of ring opening of unsubstituted cyclopropylcarbinyl radical (1a) to 3-butenyl radical (2a) and almost 106 times faster than the rate of ring opening of 1b to 2,2-dimethyl-3-butenyl radical (2c). The reasons for these unexpected findings are discussed.

Graphical abstract: Effects of geminal methyl groups on the tunnelling rates in the ring opening of cyclopropylcarbinyl radical at cryogenic temperature

Supplementary files

Article information

Article type
Communication
Submitted
23 Dec 2010
Accepted
25 Feb 2011
First published
23 Mar 2011

Org. Biomol. Chem., 2011,9, 3142-3145

Effects of geminal methyl groups on the tunnelling rates in the ring opening of cyclopropylcarbinyl radical at cryogenic temperature

X. Zhang, D. A. Hrovat, A. Datta and W. T. Borden, Org. Biomol. Chem., 2011, 9, 3142 DOI: 10.1039/C0OB01238F

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements