Strain‐driven, non‐catalysed ring expansion of silicon heterocycles

Silacycles are ubiquitous building blocks. Small silacycles can typically be expanded catalytically. A silirane, silirene and phosphasilirene as well as a siletane and a silolene were prepared starting from the base-free bromosilylene [($^{dtbp}$Cbz)SiBr] ($^{dtbp}$Cbz=1,8-bis(3,5-ditertbutylphenyl)-3,6-ditertbutylcarbazolyl). As these heterocycles were derived from a dicoordinated silylene, they are susceptible to reactions with an external base. The three-membered silacycles readily undergo non-catalysed ring expansion reactions with isonitriles yielding the related four-membered silacycles. Surprisingly, the ring-expanded derivatives of the silirane undergo up to two further isomerisation reactions, first by enamine formation and then by another ring expansion. DFT computations were utilised to gauge the scope of this reactivity pattern. Three-membered silacycles should essentially universally undergo a ring expansion with isonitriles, while for four-membered silacycles, only very few instances are predicted to accommodate more challenging kinetic requirements of this ring expansion. Larger silacycles lack the ring strain energy required for this ring expansion reaction and are not expected to be expanded.