Work

Allylic C−H Acetoxylation with a 4,5-Diazafluorenone-Ligated Palladium Catalyst: A Ligand-Based Strategy To Achieve Aerobic Catalytic Turnover

Year: 2010

Type: article

Abstract: Pd-catalyzed C-H oxidation reactions often require the use of oxidants other than O(2). Here we demonstrate a ligand-based strategy to replace benzoquinone with O(2) as the stoichiometric oxidant in Pd-catalyzed allylic C-H acetoxylation. Use of 4,5-diazafluorenone (1) as an ancillary ligand for Pd(OAc)(2) enables terminal alkenes to be converted to linear allylic acetoxylation products in good yields and selectivity under 1 atm O(2). Mechanistic studies have revealed that 1 facilitates C-O reductive elimination from a π-allyl-Pd(II) intermediate, thereby eliminating the requirement for benzoquinone in this key catalytic step.

Source: Journal of the American Chemical Society

DOI: 10.1021/ja105829t

Authors: Alison N. Campbell, Paul B. White, Ilia A. Guzei, Shannon S. Stahl

Institution: University of Wisconsin–Madison

Language: English

Topic: Oxidative Organic Chemistry Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: National Institute of General Medical Sciences, Division of Chemistry

Awards: Aerobic Oxidative Functionalization of Alkenes: Methods and Mechanisms, G1790871402, New Mechanisms for Alkene Functionalization Using Redox Active Ligands