Since its inception in 1855 with the work of Hofmann on trialkyphosphines, [1] organophosphorus chemistry has relied on the tools available for forming P À C bonds. Not surprisingly, a lot of work has been done on this topic. [2] The most recent advances concern the use of catalysts. [3] Herein, we describe a new route to PÀC bonds. The flourishing development of the chemistry of electrophilic terminal phosphinidene complexes [4] that derive from monovalent phosphorus offers the possibility of creating a new approach to P À C bonds, one that relies on the conversion of P I into P III just as the classical Arbuzov reaction relies on a P III -to-P V transformation. Unfortunately, to date, no reasonably general synthesis of PÀC bonds from phosphinidenes is available, except for a range of versatile cycloaddition reactions with unsaturated hydrocarbons. The literature contains a few reports of phosphinidene insertions into special C À H bonds [5] and two examples of reactions with soft carbon nucleophiles, that is, malonate anions [6] and stabilized phosphorus ylids. [7] Based on these last results, it appeared that the key to success was the choice of an appropriate mild carbon nucleophile. This led us to consider the possible use of the organoborates widely used in the Suzuki cross-coupling reaction. [8] Our preliminary experiments were carried out with the 7phenyl-7-phosphanorbornadiene precursor 1 a (R = Ph), [9a] phenylboronic acid 2 a (Ar = Ph), and a variety of bases. The best conditions are given in Equation (1):

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Abstract:The reaction of terminal phosphinidene complexes [RP-W(CO) 5 ] with vinylboronic acids is very sensitive to the presence or absence of solid K 3 PO 4 in suspension in the reaction medium. The products are phosphirane complexes without

Since its inception in 1855 with the work of Hofmann on trialkyphosphines, [1] organophosphorus chemistry has relied on the tools available for forming P À C bonds. Not surprisingly, a lot of work has been done on this topic. [2] The most recent advances concern the use of catalysts. [3] Herein, we describe a new route to PÀC bonds. The flourishing development of the chemistry of electrophilic terminal phosphinidene complexes [4] that derive from monovalent phosphorus offers the possibility of creating a new approach to P À C bonds, one that relies on the conversion of P I into P III just as the classical Arbuzov reaction relies on a P III -to-P V transformation. Unfortunately, to date, no reasonably general synthesis of PÀC bonds from phosphinidenes is available, except for a range of versatile cycloaddition reactions with unsaturated hydrocarbons. The literature contains a few reports of phosphinidene insertions into special C À H bonds [5] and two examples of reactions with soft carbon nucleophiles, that is, malonate anions [6] and stabilized phosphorus ylids. [7] Based on these last results, it appeared that the key to success was the choice of an appropriate mild carbon nucleophile. This led us to consider the possible use of the organoborates widely used in the Suzuki cross-coupling reaction. [8] Our preliminary experiments were carried out with the 7phenyl-7-phosphanorbornadiene precursor 1 a (R = Ph), [9a] phenylboronic acid 2 a (Ar = Ph), and a variety of bases. The best conditions are given in Equation (1):

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