Boron-based pronucleophiles in catalytic (asymmetric) C(sp3)–allyl cross-couplings

Abstract

Allylic and allenyl boronates or boranes were uncovered as suitable pronucleophiles in catalytic C–C bond formations with C(sp3) electrophiles such as O,O-acetals and N,O-aminals or ethers and carbohydrates. These transformations were most efficiently catalyzed by In(I) triflate. Importantly, chiral counteranion-directed, catalytic asymmetric allylation and allenylation of N,O-aminals was developed by employing a catalyst system composed of In(I) chloride and a chiral silver 2,2'-dihydroxy-1,1'-binaphthalene (BINOL)-phosphate.