Activation Parameters for Additions to Alkenes of Arylchlorocarbenes with Enhanced Electrophilicity

Lei Wang; Karsten Krogh-Jespersen; Robert A Moss

doi:10.1021/acs.joc.5b01210

Activation Parameters for Additions to Alkenes of Arylchlorocarbenes with Enhanced Electrophilicity

J Org Chem. 2015 Aug 7;80(15):7590-3. doi: 10.1021/acs.joc.5b01210. Epub 2015 Jul 16.

Authors

Lei Wang¹, Karsten Krogh-Jespersen¹, Robert A Moss¹

Affiliation

¹ Department of Chemistry and Chemical Biology, Rutgers University, The State University of New Jersey, New Brunswick, New Jersey 08903, United States.

PMID: 26181300
DOI: 10.1021/acs.joc.5b01210

Abstract

Activation parameters are reported for additions of phenylchlorocarbene (PhCCl), pentafluorophenylchlorocarbene (F5-PhCCl), and 3,5-dinitrophenyl-chlorocarbene (3,5-DN-PhCCl) to tetramethylethylene (TME), cyclohexene, and 1-hexene. The order of activation enthalpies is F5-PhCCl > PhCCl > 3,5-DN-PhCCl. Activation enthalpies also increase as the degree of alkene alkylation decreases. In general, the entropies of activation increase in tandem with the enthalpies of activation.