Title

Carbocations

Author ORCID Identifier

Douglas Klumpp:https://orcid.org/0000-0001-5271-699X

Publication Title

Organic Reaction Mechanisms. 2016: An Annual Survey Covering the Literature Dated January to December 2016

ISBN

9781119288657,9781119288640

Document Type

Article

Abstract

Computational studies are an essential tool in the study of carbocations. When combined with the experimental observations, theoretical work provides many useful insights into the electronic effects and structures. Among the new reactions involving carbocations, several have been developed from olefin and styrene substrates. For example, a novel catalytic method has been reported in which trityl cation salts are shown to promote the hydroarylations of alkenes. In this methodology, the trityl cation is thought to bond to the alkene substrate, creating a carbocation electrophile. This type of species then reacts with anilines to provide the hydroarylation products and regenerates the catalyst. Several reports describe superelectrophilic carbocation chemistry. A sulfur-mediated amination of olefins has been reported and a mechanism is suggested involving dicationic intermediates. A computational study examined the complexation of carbocationic species with aromatic rings, especially in the context of enzymatic stabilization of carbocations in biosynthetic transformations.

First Page

337

Last Page

367

Publication Date

1-1-2020

DOI

10.1002/9781119288657.ch6

Keywords

biosynthetic transformations, carbocation reactivity, computational study, olefin substrates, styrene substrates, superelectrophilic carbocations, trityl cation salts, vinyl carbocations

Department

Department of Chemistry and Biochemistry

COinS