Chemoselectivity in the cationic Phospha-Wittig reaction: accessing phosphorus heterocycles, phosphaalkenes, and their annulated [4 + 2] dimers.

Triflate salts of phosphito-phosphanides [LCP-P(OR)3]+ (1[OTf], R = alkyl, LC = N-heterocyclic carbene) were obtained via nucleophilic fragmentation of the tetraphosphetane [(LC)4P4][OTf]4 (3[OTf]4) with organophosphites P(OR)3. The salts 1[OTf] act as versatile reagents in the cationic Phospha-Wittig reaction, converting aldehydes into imidazoliumyl-substituted phosphaalkenes 2[OTf] and, via a competing pathway, into diphosphiranes 4[OTf]2. The product distribution is governed by the aldehyde substituent, enabling selective access to isolable derivatives of both compound classes. The resulting phosphaalkenes 2[OTf] serve as precursors to diverse phosphorus heterocycles, undergoing expected [2 + 2] dimerisation to 1,3-diphosphetanes syn/anti-(2)2[OTf]2 and trapping reactions with 1,3-dienes to yield the tetrahydrophosphinine 8[OTf] and bicyclic derivative 9[OTf]. Most notably, an unprecedented annulative [4 + 2] dimerisation pathway for cationic C-aryl phosphaalkenes is uncovered that furnishes benzannulated tetrahydro-1,2-diphosphinines 7[OTf]2. Computational studies reveal that the operative mechanism of this transformation involves a Phospha-Diels-Alder step followed by an acid-base-catalytic proton transfer, which is calculated to be energetically more accessible than the classical [2 + 2] dimerisation.