Development, mechanism, and scope of the palladium-catalyzed enantioselective allene diboration.
In the presence of a chiral phosphoramidite ligand, the palladium-catalyzed diboration of allenes can be executed with high enantioselectivity. This reaction provides high levels of selectivity with a range of aromatic and aliphatic allene substrates. Isotopic-labeling experiments, stereodifferentiating reactions, kinetic analysis, and computational experiments suggest that the catalytic cycle proceeds by a mechanism involving rate-determining oxidative addition of the diboron to Pd followed by transfer of both boron groups to the unsaturated substrate. This transfer reaction most likely occurs by coordination and insertion of the more accessible terminal alkene of the allene substrate, by a mechanism that directly provides the eta3 pi-allyl complex in a stereospecific, concerted fashion.
Burks
Heather E
HE
Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
Liu
Shubin
S
Morken
James P
JP
D000466:Alkadienes / Q000737:chemistry*; D001895:Boron / Q000737:chemistry; D001896:Boron Compounds / Q000138:chemical synthesis*; D002384:Catalysis; D006841:Hydrocarbons, Aromatic / Q000737:chemistry; D009930:Organic Chemicals / Q000138:chemical synthesis; D010165:Palladium
D000466:Alkadienes; D001896:Boron Compounds; D006841:Hydrocarbons, Aromatic; D009930:Organic Chemicals; D010165:Palladium; D001895:Boron