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  • Manuscript_CAissa_jo-2019-03032h

    Rights statement: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Organic Chemistry, copyright ©2019 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/abs/10.1021/acs.joc.9b03032

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Palladium-Catalyzed Synthesis of α-Carbonyl-α′-(hetero)aryl Sulfoxonium Ylides: Scope and Insight into the Mechanism

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<mark>Journal publication date</mark>1/01/2020
<mark>Journal</mark>Journal of Organic Chemistry
Issue number2
Volume85
Number of pages12
Pages (from-to)1126-1137
Publication StatusPublished
Early online date6/12/19
<mark>Original language</mark>English

Abstract

Despite recent advances, a general method for the synthesis of α-carbonyl-α′-(hetero)aryl sulfoxonium ylides is needed to benefit more greatly from the potential safety advantages offered by these compounds over the parent diazo compounds. Herein, we report the palladium-catalyzed cross-coupling of aryl bromides and triflates with α-carbonyl sulfoxonium ylides. We also report the use of this method for the modification of an active pharmaceutical ingredient and for the synthesis of a key precursor of antagonists of the neurokinin-1 receptor. In addition, the mechanism of the reaction was inferred from several observations. Thus, the oxidative addition complex [(XPhos)PhPdBr] and its dimer were observed by 31P{1H} NMR, and these complexes were shown to be catalytically and kinetically competent. Moreover, a complex resulting from the transmetalation of [(XPhos)ArPdBr] (Ar = p-CF3–C6H4) with a model sulfoxonium ylide was observed by mass spectrometry. Finally, the partial rate law suggests that the transmetalation and the subsequent deprotonation are rate-determining in the catalytic cycle.

Bibliographic note

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Organic Chemistry, copyright ©2019 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/abs/10.1021/acs.joc.9b03032