The first example of Ir-catalyzed asymmetric substitution reaction with vinyl trifluoroborates is described. The direct reaction between branched, racemic allylic alcohols and potassium alkenyltrifluoroborates proceeded with high site selectivity and excellent enantioselectivity (up to 99%) mediated by an Ir-(P,olefin) complex. This method allows rapid access to various 1,4-dienes or trienes including the biologically active natural products (-)-nyasol and (-)-hinokiresinol.

The direct Ir-catalyzed cross-coupling between branched, racemic allylic alcohols and simple olefins is described. This transformation is catalyzed by an Ir-(P,olefin) complex and proceeds with high site selectivity and excellent enantioselectivity. The method allows rapid access to various 1,5-dienes or trienes and was used in the catalytic asymmetric synthesis of the γ-secretase modulator JNJ-40418677.

No leaving group needed: With an Ir(P,olefin) complex as catalyst, the direct enantioselective allylic alkynylation of secondary allylic alcohols with potassium alkynyltrifluoroborates as alkynylating reagents has been achieved. High levels of enantioselectivity and high yields were achieved with this operationally easy and robust protocol, the use of which was demonstrated in the synthesis of GPR40 receptor agonist AMG 837. cod = 1,5-cyclooctadiene.