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Reaction of an N-heterocyclic carbene-stabilized silicon(II) monohydride with alkynes: [2+2+1] cycloaddition versus
Carsten Eisenhut1, Tibor Szilvási, Nora C Breit
1Department of Chemistry, Technische Universität Berlin, Straße des 17. Juni 135, Sekr. C2, 10623 Berlin (Germany), Fax: (+49) 30-314-29732.
Abstract:
An in depth study of the reactivity of an N-heterocyclic carbene (NHC)-stabilized silylene monohydride with alkynes is reported. The reaction of silylene monohydride 1, tBu3 Si(H)Si←NHC, with diphenylacetylene afforded silole 2, tBu3 Si(H)Si(C4 Ph4 ). The density functional theory (DFT) calculations for the reaction mechanism of the [2+2+1] cycloaddition revealed that the NHC played a major part stabilizing zwitterionic transition states and intermediates to assist the cyclization pathway. A significantly different outcome was observed, when silylene monohydride 1 was treated with phenylacetylene, which gave rise to supersilyl substituted 1-alkenyl-1-alkynylsilane 3, tBu3 Si(H)Si(CHCHPh)(CCPh). Mechanistic investigations using an isotope labelling technique and DFT calculations suggest that this reaction occurs through a similar zwitterionic intermediate and subsequent hydrogen abstraction from a second molecule of phenylacetylene.
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One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
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