Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 54, Issue 41, Pages 12158-12162Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201504941
Keywords
alkenes; boron; density functional calculations; hydrogenation; Lewis acids
Categories
Funding
- Deutsche Forschungsgemeinschaft [EXC 314/2]
- [SFB 813]
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A transition-metal-free transfer hydrogenation of 1,1-disubstituted alkenes with cyclohexa-1,4-dienes as the formal source of dihydrogen is reported. The process is initiated by B(C6F5)(3)-mediated hydride abstraction from the dihydrogen surrogate, forming a Bronsted acidic Wheland complex and [HB(C6F5)(3)](-). A sequence of proton and hydride transfers onto the alkene substrate then yields the alkane. Although several carbenium ion intermediates are involved, competing reaction channels, such as dihydrogen release and cationic dimerization of reactants, are largely suppressed by the use of a cyclohexa-1,4-diene with methyl groups at the C1 and C5 as well as at the C3 position, the site of hydride abstraction. The alkene concentration is another crucial factor. The various reaction pathways were computationally analyzed, leading to a mechanistic picture that is in full agreement with the experimental observations.
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