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Ionic-Type Reactivity of 1,3-Dibora-2,4-diphosphoniocyclobutane-1,3-diyls: Regio- and Stereoselective Addition of Hydracids

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posted on 30.09.2009, 00:00 authored by Gad Fuks, Nathalie Saffon, Laurent Maron, Guy Bertrand, Didier Bourissou
Hydrogen chloride and trifluoromethane sulfonic acid readily add to the symmetrically substituted 1,3-dibora-2,4-diphosphoniocyclobutane-1,3-diyl (1) and unsymmetrically substituted 1,3-dibora-2,4-diphosphoniobicyclo[1.1.0]butane (3) under mild conditions, substantiating some formal analogies between the PBPB diradicaloids D and alkenes. X-ray diffraction analyses carried out on all the resulting 1,3-diborata-2,4-diphosphoniocyclobutanes (2, 4−6) revealed that the reactions proceed with complete stereo- and regio-selectivity, and that an unusual t-Bu → i-Bu isomerization can occur at boron. DFT calculations shed more light on the factors controlling the regioselectivity of the additions, its concerted versus stepwise character, and support an original two-step mechanism for the t-Bu → i-Bu isomerization, involving a carbocationic σ-borane adduct as a key intermediate.