Intramolecular oxyacylation of alkenes using a hydroxyl directing group

Giang T. Hoang, Zhongda Pan, Jason T. Brethorst, Christopher J. Douglas

Research output: Contribution to journalArticlepeer-review

11 Scopus citations

Abstract

Alkene oxyacylation is a new strategy for the preparation of β-oxygenated ketones. Now, with Ir catalysis and low-cost salicylate esters, alkene oxyacylation can be promoted by simple and versatile hydroxyl directing groups. This paper discusses catalyst optimization, substituent effects, mechanistic experiments, and the challenges associated with asymmetric catalysis. Crossover experiments point to several key steps of the mechanism being reversible, including the most likely enantiodetermining steps. The oxyacylation products are also prone to racemization without catalyst when heated alone; however, crossover is not observed without catalyst. These observations account for the low levels of enantioinduction in alkene oxyacylation. The versatility of the hydroxyl directing group is highlighted by demonstrating further transformations of the products.

Original languageEnglish (US)
Pages (from-to)11383-11394
Number of pages12
JournalJournal of Organic Chemistry
Volume79
Issue number23
DOIs
StatePublished - Dec 5 2014

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