Nucleophilic activation of alkenyl and aryl boronates by a chiral Cu(I)F complex: catalytic enantioselective alkenylation and arylation of aldehydes.
A new method for the catalytic enantioselective alkenylation and arylation of aldehydes involves the activation of alkenyl and aryl boronates by a catalytic amount of the Cu(I)F-DTBM-segphos complex through transmetalation, generating novel alkenyl and aryl copper species. These reagents act as the actual nucleophile. A range of aldehydes can be converted into optically active secondary allyl alcohols or diaryl methanols with excellent enantioselectivity. The appropriate choice of additives, depending on the substrate, is critical to ensure high yields of products. These additives possibly modulate the catalyst turnover step from copper alkoxide intermediates generated by the addition of organocopper reagents to aldehydes.
Tomita
Daisuke
D
Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Kanai
Motomu
M
Shibasaki
Masakatsu
M
D000447:Aldehydes / Q000737:chemistry*; D001897:Boronic Acids / Q000737:chemistry*; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D005459:Fluorides / Q000737:chemistry*; D013237:Stereoisomerism
D000447:Aldehydes; D001897:Boronic Acids; C057829:copper fluoride; D003300:Copper; D005459:Fluorides