Regio- and stereoselective Ni-catalyzed 1,4-hydroboration of 1,3-dienes: access to stereodefined (Z)-allylboron reagents and derived allylic alcohols.
A catalytic regio- and stereoselective 1,4-hydroboration of 1,3-dienes was accomplished with pinacolborane in the presence of Ni(cod)(2) and PCy(3). This reaction exhibits broad substrate scope operating on a range of substituted dienes and occurs with generally high levels of selectivity and efficiency. Reactivity patterns suggest that the reactive conformation of the diene is the S-cis form. The intermediate allylboronate can be oxidized to stereodefined allylic alcohols or can be used in stereoselective carbonyl addition reactions.
Ely
Robert J
RJ
Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
Morken
James P
JP
D000498:Allyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D001896:Boron Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D009532:Nickel / Q000737:chemistry*; D020005:Propanols / Q000138:chemical synthesis / Q000737:chemistry; D013237:Stereoisomerism
D000498:Allyl Compounds; D001896:Boron Compounds; D020005:Propanols; C006463:allyl alcohol; D009532:Nickel