α‐Arylation by Rearrangement: On the Reaction of Enolates with Diaryliodonium Salts

Abstract

Surprising equilibration: A new mechanism for the title reaction is supported by DFT calculations and experimental observations. The CI and OI intermediates are isoenergetic and equilibrate quickly. Thus, any chiral information induced in the initial complex will be destroyed. In the final CC bond-forming step, a [2,3]-rearrangement from the OI bonded intermediate is slightly preferred over the [1,2]-elimination from the CI bonded isomer (see scheme). Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.