Janot, Christopher, Chagnoleau, Jean-Baptiste, Halcovitch, Nathan R, Muir, James and Aissa, Christophe 
ORCID: 0000-0003-0750-9435
(2020)
Palladium-Catalyzed Synthesis of α-Carbonyl-α′-(hetero)aryl Sulfoxonium Ylides: Scope and Insight into the Mechanism.
JOURNAL OF ORGANIC CHEMISTRY, 85 (2).
pp. 1126-1137.
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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 <sup>31</sup>P{<sup>1</sup>H} NMR, and these complexes were shown to be catalytically and kinetically competent. Moreover, a complex resulting from the transmetalation of [(XPhos)ArPdBr] (Ar = <i>p</i>-CF<sub>3</sub>-C<sub>6</sub>H<sub>4</sub>) 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.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | Rare Diseases |
| Depositing User: | Symplectic Admin |
| Date Deposited: | 19 Dec 2019 15:19 |
| Last Modified: | 14 Mar 2024 18:28 |
| DOI: | 10.1021/acs.joc.9b03032 |
| Related URLs: | |
| URI: | https://livrepository.liverpool.ac.uk/id/eprint/3067082 |
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