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J Org Chem. 2013 Feb 1;78(3):844-54. doi: 10.1021/jo3027824. Epub 2013 Jan 23.

Palladium-catalyzed cross-coupling of aziridinylmetal species, generated by sulfinyl-magnesium exchange, with aryl bromides: reaction optimization, scope, and kinetic investigations.

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1
Department of Chemistry, Imperial College London, South Kensington, London SW7 2AZ, UK.

Abstract

A series of novel, highly substituted N-PMP aziridines have been accessed in high yields by palladium-catalyzed cross-coupling of intact aziridines. The cross-coupling employed aryl bromides and tertiary organometallic aziridines, generated from sulfinylaziridines by sulfinyl-magnesium exchange and transmetalation to the aziridinylzinc with zinc chloride. A wide range of electron-rich and electron-poor aryl bromides were utilized to afford the functionalized aziridine products as single diastereoisomers with retention of configuration at the reacting center. Assessment of the reaction kinetics showed zero-order in both the aziridine species and the aryl bromide. This indicated that the rate-determining step was reductive elimination from the palladium(II) species bearing both the aziridine and aryl groups to form the hindered C-C bond. The intermediate aziridinylzinc species underwent a progressive, background degradation that led to a plateau in yield and afforded reduced yields in substrates with ortho-substituted aryl groups, which are less reactive due to the additional steric demands.

PMID:
23311879
DOI:
10.1021/jo3027824
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