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

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Title Generation and Trapping of a Cage Annulated Vinylidenecarbene and Approaches to Its Cycloalkyne Isomer
 
Creator SAHU, B
GURURAJA, GN
KUMAR, T
CHATTERJEE, A
GANGULY, B
MOBIN, SM
NAMBOOTHIRI, INN
 
Subject BUTTENBERG-WIECHELL REARRANGEMENT
ORGANIC-SYNTHESIS
POLYCYCLIC SYSTEMS
CYCLOPENTYNE
CARBENES
SINGLET
CYCLOADDITION
CYCLOBUTYNE
DERIVATIVES
POLYYNES
 
Description 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-a-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.
 
Publisher AMER CHEMICAL SOC
 
Date 2014-10-15T10:42:18Z
2014-10-15T10:42:18Z
2012
 
Type Article
 
Identifier JOURNAL OF ORGANIC CHEMISTRY, 77(16)6998-7004
http://dx.doi.org/10.1021/jo301215d
http://dspace.library.iitb.ac.in/jspui/handle/100/14773
 
Language en