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Non-Directed Allylic C–H Acetoxylation in the Presence of Lewis Basic Heterocycles

Malik, Hasnain and Taylor, Buck and Kerrigan, John and Grob, Jonathan and Houk, Ken and Du Bois, Justin and Hamann, Lawrence and Patterson, Andrew (2014) Non-Directed Allylic C–H Acetoxylation in the Presence of Lewis Basic Heterocycles. Chemical Science.

Abstract

We outline a strategy to enable non-directed Pd(II)-catalyzed C–H functionalization in the presence of Lewis basic heterocycles. In a high-throughput screen of two Pd-catalyzed C–H acetoxylation reactions, addition of a variety of N-containing heterocycles is found to cause low product conversion. A pyridine-containing test substrate is selected as representative of heterocyclic scaffolds that are hypothesized to cause catalyst arrest. We pursue two approaches in parallel that allow product conversion in this representative system: Lewis acids are found to be effective in situ blocking groups for the Lewis basic site, and a pre-formed pyridine N-oxide is shown to enable high yield of allylic C–H acetoxylation. Computational studies with density functional theory (M06) of binding affinities of selected heterocycles to Pd(OAc)2 provide an inverse correlation of the computed heterocycle–Pd(OAc)2 binding affinities with the experimental conversions to products. Additionally, 1H NMR binding studies provide experimental support for theoretical calculations.

Item Type: Article
Additional Information: This is all basic research with no IP protected compounds used. Most compounds were purchased from Sigma or were made using literature procedures and are not mean to be novel in any way.
Date Deposited: 13 Oct 2015 13:13
Last Modified: 13 Oct 2015 13:13
URI: https://oak.novartis.com/id/eprint/11149

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