Reactivity of Phenylacetylene toward Unsymmetrical Disilenes: Regiodivergent [2+2] Cycloaddition vs. CH Addition

Abstract

We report the regiodivergent reaction of phenylacetylene with a selection of disilenes Tip 2 Si=SiTipR as well as bridged tetrasiladienes Tip 2 Si=SiTipÀ LUÀ SiTip=SiTip 2 (Tip = 2,4,6-i Pr 3 C 6 H 2 , R = aryl groups; LU = arylene linkers). The regioselectivity of the [2 + 2] cycloaddition as determined by NMR spectroscopy and X-ray crystallography is shown to strongly depend on the nature of the substituent R. The small size of the substituents compared to the Tip groups in both cases suggests a change in mechanism between the substrates with only hydrogen in the ortho-positions of R and LU and those with either ortho-methyl groups or condensed aromatic rings. In contrast, the presence of catalytic quantities of base completely suppresses cycloaddtion in favor of the formal CH addition of phenylacetylene. Quenching reactions with either MeI or MeOH after the stoichiometric application of deprotonated phenylacetylene as well as NMR studies at low temperature prove the intermediacy of an alkynyl-substituted disilanyl lithium and thus suggest a carbolithiation pathway for the net CH addition.