The phosphinoboration of acyl chlorides

Maia C Murphy; Alina Trofimova; James H W LaFortune; Christopher M Vogels; Stephen J Geier; Justin F Binder; Charles L B Macdonald; Douglas W Stephan; Stephen A Westcott

doi:10.1039/d0dt00579g

The phosphinoboration of acyl chlorides

Dalton Trans. 2020 Apr 28;49(16):5092-5099. doi: 10.1039/d0dt00579g.

Authors

Maia C Murphy¹, Alina Trofimova², James H W LaFortune², Christopher M Vogels¹, Stephen J Geier¹, Justin F Binder³, Charles L B Macdonald³, Douglas W Stephan², Stephen A Westcott¹

Affiliations

¹ Department of Chemistry and Biochemistry, Mount Allison University, Sackville, NB E4L 1G8, Canada. swestcott@mta.ca.
² Department of Chemistry, University of Toronto, Toronto, ON M5S 3H6, Canada.
³ Department of Chemistry and Biochemistry, University of Windsor, Windsor, ON N9B 3P4, Canada. douglas.stephan@utoronto.ca and Department of Chemistry, Carleton University, Ottawa, ON K1S 5B6, Canada.

PMID: 32167110
DOI: 10.1039/d0dt00579g

Abstract

This investigation examines the reactivity of phosphinoboronate esters Ph2PBpin (pin = 1,2-O2C2Me4) and Ph2PBcat (cat = 1,2-O2C6H4), as well as other phosphinoboron species, with various aryl and aliphatic acyl chlorides. These reactions proceed smoothly to give acyl phosphines of the type RC(O)PR'2 along with loss of a boron-chloride compound. In some cases, a second equivalent of the phosphinoboron species can add to the C[double bond, length as m-dash]O double bond at elevated temperatures to give the corresponding diphosphines RC(OBR''2)(PR'2)2. These ambiphilic diphosphines behave like substituted (1,1-bis(diphenylphosphino)methane) derivatives in a reaction of PhC(OBpin)(PPh2)2 (2a) with (η5-C9H7)Rh(η2-coe)2 (coe = cis-cyclooctene) affording the indenyl rhodium complex (η5-C9H7)Rh(PhC(OBpin)(PPh2)2) (3a) where the phosphines are bound to the metal centre in a κ2-P,P bidentate manner.