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. 2021 Oct 27;143(42):17825-17832.
doi: 10.1021/jacs.1c09175. Epub 2021 Oct 13.

Manganese-Catalyzed Dehydrogenative Silylation of Alkenes Following Two Parallel Inner-Sphere Pathways

Stefan Weber  1 , Manuel Glavic  1 , Berthold Stöger  2 , Ernst Pittenauer  3 , Maren Podewitz  4 , Luis F Veiros  5 , Karl Kirchner  1
Affiliations

Manganese-Catalyzed Dehydrogenative Silylation of Alkenes Following Two Parallel Inner-Sphere Pathways

Stefan Weber et al. J Am Chem Soc. .

Abstract

We report on an additive-free Mn(I)-catalyzed dehydrogenative silylation of terminal alkenes. The most active precatalyst is the bench-stable alkyl bisphosphine Mn(I) complex fac-[Mn(dippe)(CO)3(CH2CH2CH3)]. The catalytic process is initiated by migratory insertion of a CO ligand into the Mn-alkyl bond to yield an acyl intermediate which undergoes 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 efficiently and selectively converted into E-vinylsilanes and allylsilanes, respectively, at room temperature. Mechanistic insights are provided based on experimental data and DFT calculations 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.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Manganese-Catalyzed DS of Alkenes
Scheme 2
Scheme 2. Formation of the Active Species via Migratory Insertion and Deprotonation of the Entering Ligand
Scheme 3
Scheme 3. Kinetic Profile and Mechanistic Experiments
Scheme 4
Scheme 4. Determination of KIE and Deuterium Incorporation
Scheme 5
Scheme 5. Stochiometric Reaction of 1 with HSiPhMe2
Figure 1
Figure 1
Free energy profile calculated at M06/6-311++G**//PBE0/SDD,6-31G** level for the formation of [Mn(dippe)(CO)2(SiMe3)(η2-CH2=CHCH3)] (A) and the E-Vinylsilene Intermediate [Mn(dippe)(CO)2(η2-CH(SiMe3)=CHCH3)] (DE). Free Energies (kcal/mol) are referred to A.
Figure 2
Figure 2
Free energy profile calculated at M06/6-311++G**//PBE0/SDD,6-31G** level for the acceptorless DS and classic DS pathways from intermediate DE. Free Energies (kcal/mol) are referred to A.
Scheme 6
Scheme 6. Proposed Mechanism for DS Following Two Parallel Pathways
See this image and copyright information in PMC

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