二座ホスホロアミダイト配位子を用いる有機ホウ素化合物の不斉付加反応

抄録

The transition metal catalyzed addition reactions of organic electrophiles to activated alkenes, imines and carbonyl compounds are powerful tools for new carbon-carbon bonds with high enantioselectivity. Chiral bidentate phosphoramidite ligands (Me-BIPAM and N-Me-BIPAM) were synthesized from linked-BINOL as new ligands for asymmetric addition reactions of arylboronic acids. These bidentate phosphoramidite ligands appear to be highly effective for rhodium-catalyzed asymmetric conjugate addition of arylboronic acids to α,β-unsaturated ketones. In the course of our study on bidentate phosphoramidites as a chiral ligand for enantioselective bond-forming reactions, we found that N-Me-BIPAM is effective for arylation of N-sulfonyl arylimines with arylboronic acids. Me-BIPAM was found to be highly efficient for ruthenium-catalyzed enantioselective arylation of aldehydes, α-ketoesters, glyoxylate, and isatins. In this review, we focus on chiral bidentate phosphoramidite ligands (Me-BIPAM and N-Me-BIPAM) for asymmetric carbon-carbon bond-forming reactions of arylboronic acids.