Diels-Alder reactions of 1-phosphabutadienes: a highly selective route to P[double bond, length as m-dash]C-substituted phosphacyclohexenes

Kazuaki Ohtsuki; Henry T G Walsgrove; Yoshihiro Hayashi; Susumu Kawauchi; Brian O Patrick; Derek P Gates; Shigekazu Ito

doi:10.1039/c9cc08997g

Diels-Alder reactions of 1-phosphabutadienes: a highly selective route to P[double bond, length as m-dash]C-substituted phosphacyclohexenes

Chem Commun (Camb). 2020 Jan 16;56(5):774-777. doi: 10.1039/c9cc08997g. Epub 2019 Dec 17.

Authors

Kazuaki Ohtsuki¹, Henry T G Walsgrove², Yoshihiro Hayashi¹, Susumu Kawauchi¹, Brian O Patrick², Derek P Gates², Shigekazu Ito¹

Affiliations

¹ School of Materials and Chemical Technology, Tokyo Institute of Technology, 2-12-1-H113 Ookayama, Meguro, Tokyo 152-8552, Japan. ito.s.ao@m.titech.ac.jp.
² Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC V6T 1Z1, Canada. dgates@chem.ubc.ca.

PMID: 31845681
DOI: 10.1039/c9cc08997g

Abstract

Kinetically stabilized 1-phosphahaloprenes (2-halo-1-phosphabutadienes) as well as 1-phosphaisoprene undergo a hitherto unknown phospha-Diels-Alder dimerization of the P[double bond, length as m-dash]C-C[double bond, length as m-dash]C units upon heating. The [4+2] cyclodimerization is highly stereo- and regio-selective. The phosphaalkene-substituted phosphacyclohexene product is an unprecedented P(sp²),P(sp³) ligand that is of interest in polymer/materials science and catalysis.