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Hydroboration of Terminal Alkenes and trans-1,2-Diboration of Terminal Alkynes Catalyzed by a Manganese(I) Alkyl Complex.


ABSTRACT: 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)],

SUBMITTER: Weber S 

PROVIDER: S-EPMC10947181 | biostudies-literature | 2021 Nov

REPOSITORIES: biostudies-literature