Tertiary alcohols by tandem β-carbolithiation and N→C aryl migration in enol carbamates

Anne M. Fournier, Jonathan Clayden*

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

28 Citations (Scopus)

Abstract

Enol carbamates (O-vinylcarbamates) derived from aromatic or α,β-unsaturated compounds and bearing an N-aryl substituent undergo carbolithiation by nucleophilic attack at the (nominally nucleophilic) β position of the enol double bond. The resulting carbamate-stabilized allylic, propargylic, or benzylic organolithium rearranges with N→C migration of the N-aryl substituent, creating a quaternary carbon α to O. The products may be readily hydrolyzed to yield multiply branched tertiary alcohols in a one-pot tandem reaction, effectively a polarity-reversed nucleophilic β-alkylation-electrophilic α-arylation of an enol equivalent.

Original languageEnglish
Pages (from-to)142-145
Number of pages4
JournalOrganic Letters
Volume14
Issue number1
Early online date29 Nov 2011
DOIs
Publication statusPublished - 6 Jan 2012

Fingerprint

Dive into the research topics of 'Tertiary alcohols by tandem β-carbolithiation and N→C aryl migration in enol carbamates'. Together they form a unique fingerprint.

Cite this