Hydroboration of Terminal Alkenes and trans ‐1,2‐Diboration of Terminal Alkynes Catalyzed by a Manganese(I) Alkyl Complex
Autor: | Luis Filipe Veiros, Stefan Weber, Daniel Patrick Zobernig, Karl Kirchner, Berthold Stöger |
---|---|
Rok vydání: | 2021 |
Předmět: |
chemistry.chemical_classification
alkenes Ligand Communication Acetylide Migratory insertion General Chemistry General Medicine alkynes Medicinal chemistry Catalysis Communications Hydroboration chemistry.chemical_compound chemistry hydroboration Yield (chemistry) Homogeneous Catalysis | Hot Paper 1 2-diboration manganese alkyl complex Alkyl Bond cleavage |
Zdroj: | Angewandte Chemie (International Ed. in English) |
ISSN: | 1521-3757 0044-8249 |
Popis: | A MnI‐catalyzed hydroboration of terminal alkenes and a 1,2‐diboration of terminal alkynes with pinacolborane (HBPin) is described. For alkenes, anti‐Markovnikov hydroboration takes place; for alkynes the reaction proceeds with excellent trans‐1,2‐selectivity. The most active pre‐catalyst is bench‐stable alkyl bisphosphine MnI 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 B−H bond cleavage of HBPin (for alkenes) and rapid C−H bond cleavage (for alkynes), forming the active MnI boryl and acetylide catalysts [Mn(dippe)(CO)2(BPin)] and [Mn(dippe)(CO)2(C≡CR)], respectively. A broad variety of aromatic and aliphatic alkenes and alkynes was efficiently and selectively borylated. Mechanistic insights are provided based on experimental data and DFT calculations revealing that an acceptorless reaction is operating involving dihydrogen release. A MnI‐catalyzed hydroboration of terminal alkenes and the 1,2‐diboration of terminal alkynes with pinacolborane is described. In the case of alkenes anti‐Markovnikov hydroboration takes place, while in the case of alkynes the reaction proceeds with trans‐1,2‐selectivity. |
Databáze: | OpenAIRE |
Externí odkaz: |