Phosphorus compounds with unusual coordination. 45. A 1-silyl-1H-phosphinene/1,2-dihydro-1,2-phosphasilete rearrangement: the decisive stop in the synthesis of heterocycles with a 2-phospha-1,3-diene moiety.
Tris(trimethylsilyl)silyl-1H-phosphirene I underwent photochem. ring enlargement to dihydrophosphasilete II (R = SiMe3). The reactivity of II (R = SiMe3) was explored by reaction with a) ClP: CSiMe3 in ether to give II (R = P:CSiMe3); b) HC.tplbond.CCO2Me in ether to give II [R = CH:C(CO2Me)SiMe3]; c) Ph2C:C:O to give II [R = C(OSiMe3):CPh2]; and d) R1C(O)Cl to give III (R1 = CMe3 or ferrocenyl).
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