Intermolecular zirconium-catalyzed hydrophosphination of alkenes and dienes with primary phosphines

Michael B Ghebreab; Christine A Bange; Rory Waterman

doi:10.1021/ja503036z

Intermolecular zirconium-catalyzed hydrophosphination of alkenes and dienes with primary phosphines

J Am Chem Soc. 2014 Jul 2;136(26):9240-3. doi: 10.1021/ja503036z. Epub 2014 Jun 20.

Authors

Michael B Ghebreab¹, Christine A Bange, Rory Waterman

Affiliation

¹ Department of Chemistry, University of Vermont , Burlington, Vermont 05405, United States.

PMID: 24937212
DOI: 10.1021/ja503036z

Abstract

Catalytic hydrophosphination of terminal alkenes and dienes with primary phosphines (RPH2; R = Cy, Ph) under mild conditions has been demonstrated using a zirconium complex, [κ(5)-N,N,N,N,C-(Me3SiNCH2CH2)2NCH2CH2NSiMe2CH]Zr (1). Exclusively anti-Markovnikov functionalized products were observed, and the catalysis is selective for either the secondary or tertiary phosphine (i.e., double hydrophosphination) products, depending on reaction conditions. The utility of the secondary phosphine products as substrates for further elaboration was demonstrated with a platinum-catalyzed asymmetric alkylation reaction.