Enantioselective conjugate silyl additions to α,β-unsaturated aldehydes catalyzed by combination of transition metal and chiral amine catalysts

• We report that transition metal-catalyzed nucleophilic activation can be combined with chiral amine-catalyzed iminium activation as exemplified by the unprecedented enantioselective conjugate addition of a dimethylsilanyl group to α,β-unsaturated aldehydes. These reactions proceed with excellent 1,4-selectivity to afford the corresponding β-silyl aldehyde products 3 in high yields and up to 97:3 er using inexpensive bench stable copper salts and simple chiral amine catalysts. The reaction canalso generate a quaternary stereocenter with goodenantioselectivity. Density functional calculations are performed to elucidate the reaction mechanism and the origin of enantioselectivity.

Subject headings

NATURVETENSKAP  -- Kemi -- Organisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Organic Chemistry (hsv//eng)

Keyword

asymmetric catalysis

organocatalysis

bsilyl aldehydes

transition metal catalysis

α

β-unsaturated aldehydes

Organic chemistry

Organisk kemi

Publication and Content Type

ref (subject category)

art (subject category)