Manganese-Catalyzed Dehydrogenative Silylation of Alkenes Following Two Paral-lel Pathways

12 July 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

We report on an additive-free Mn(I)-catalyzed dehydrogenative silylation of terminal alkenes. The most active pre-catalyst is the bench-stable alkyl bisphosphine Mn(I) complex fac-[Mn(dippe)(CO)3(CH2CH2CH3)]. The catalytic pro-cess is initiated by migratory insertion of a CO ligand into the Mn-alkyl bond to yield an acyl intermediate which un-dergoes rapid Si-H bond cleavage of the silane HSiR3 forming the active 16e- Mn(I) silyl catalyst [Mn(dippe)(CO)2(SiR3)] together with liberated butanal. A broad variety of aromatic and aliphatic alkenes was efficient-ly and selectively converted into E-vinylsilanes and allylsilanes, respectively, at room temperature. Mechanistic insights are provided based on experimental data revealing that two parallel reaction pathways are operative: an acceptorless reaction pathway involving dihydrogen release and a pathway requiring an alkene as sacrificial hydrogen acceptor.

Keywords

manganese
dehydrogenative silylation
alkenes
alkyl complexes

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