The formation of cage phosphoranes and their rearrangements in the reactions of substituted 2-(3-oxo-3-phenyl)ethoxybenzo[d]-1,3,2-dioxaphospholes with perfluorodiacetyl

Vladimir F Mironov; Mudaris N Dimukhametov; Gulnara A Ivkova; Khasan R Khayarov; Daut R Islamov; Igor A Litvinov

doi:10.1039/d1cc02941j

The formation of cage phosphoranes and their rearrangements in the reactions of substituted 2-(3-oxo-3-phenyl)ethoxybenzo[d]-1,3,2-dioxaphospholes with perfluorodiacetyl

Chem Commun (Camb). 2021 Sep 4;57(68):8516-8519. doi: 10.1039/d1cc02941j. Epub 2021 Aug 5.

Authors

Vladimir F Mironov¹, Mudaris N Dimukhametov, Gulnara A Ivkova, Khasan R Khayarov, Daut R Islamov, Igor A Litvinov

Affiliation

¹ A.E.Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Arbuzov Str. 8, Kazan 420088, Russia. mironov@iopc.ru.

PMID: 34352057
DOI: 10.1039/d1cc02941j

Abstract

The Kukhtin-Ramirez reaction of 2-(3-oxo-3-phenyl)ethoxy-benzo[d]-1,3,2-dioxaphospholes with perfluorodiacetyl was monitored by NMR methods. To our surprise the initial stage involved a kinetically controlled [4+4]-cycloaddition with the formation of a cage phosphorane containing a 2',5',8',9'-tetraoxa-2λ⁵-phosphaspiro[benzo[d][1,3,2]dioxaphosphole-2,1'-bicyclo[4.2.1]nonan]-3'-ene (compound 5) scaffold. Intermediate 5 then converts to spirophosphorane-4',5'-bis(trifluoromethyl)-2λ⁵-spiro[benzo[d] [1,3,2]dioxaphosphole-2-yl-2,2'-[1,3,2] dioxaphosphole (compound 4). Compound 4 further rearranges into a cage phosphorane derivative containing a [2,5]epoxybenzo[d][1,3,6,2]trioxaphosphocine] (compound 3) backbone.