Generation and Trapping of a Cage Annulated Vinylidenecarbene and Approaches to Its Cycloalkyne Isomer

Sahu, Bichismitha ; Gururaja, Guddeangadi N. ; Kumar, Tarun ; Chatterjee, Anamitra ; Ganguly, Bishwajit ; Mobin, Shaikh M. ; Namboothiri, Irishi N. N. (2012) Generation and Trapping of a Cage Annulated Vinylidenecarbene and Approaches to Its Cycloalkyne Isomer Journal of Organic Chemistry, 77 (16). pp. 6998-7004. ISSN 0022-3263

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Official URL: http://doi.org/10.1021/jo301215d

Related URL: http://dx.doi.org/10.1021/jo301215d

Abstract

A novel cage-annulated (bis-homocubyl) vinylidenecarbene has been generated and successfully trapped without any intermediacy of its cycloalkyne isomer. The greater kinetic and thermodynamic stability of the vinylidenecarbene vis-à-vis its cycloalkyne isomer has been predicted by DFT B3LYP/6-31G* calculations. The calculated results suggest the prospects of the cycloalkyne becoming amenable for trapping, if generated under suitable experimental conditions, owing to the substantial kinetic energy barrier associated with its possible ring contraction via 1,2-shift to the vinylidenecarbene isomer and marginal ground state energy difference. However, all of our attempts to directly generate and trap the cycloalkyne yielded unsatisfactory results. Attempted generation and trapping of a C2-symmetric bis-vinylidenecarbene from a bis-vinylidenedibromide met with unexpected failure.

Item Type:Article
Source:Copyright of this article belongs to American Chemical Society.
ID Code:121565
Deposited On:19 Jul 2021 09:10
Last Modified:19 Jul 2021 09:10

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