Anyu He

Stereospecific Suzuki Cross-Coupling of Alkyl α-Cyanohydrin Triflates

Scalemic alpha-cyanohydrin triflates undergo Pd-catalyzed cross-coupling with aryl, heteroaryl, and vinyl boronic acids under mild conditions. Coupling proceeds with complete inversion of configuration at the stereogenic carbon. The resultant nitrile can be easily converted into a variety of alternative functional groups of value in organic synthesis and thus achieves a higher level of molecular complexity than the products of traditional Suzuki reactions.

Enantioselective, Organocatalytic Reduction of Ketones using Bifunctional Thiourea-Amine Catalysts

Prochiral ketones are reduced to enantioenriched, secondary alcohols using catecholborane and a family of air-stable, bifunctional thiourea-amine organocatalysts. Asymmetric induction is proposed to arise from the in situ complexation between the borane and chiral thiourea-amine organocatalyst resulting in a stereochemically biased boronate-amine complex. The hydride in the complex is endowed with enhanced nucleophilicity while the thiourea concomitantly embraces and activates the carbonyl.

Pd-catalyzed cross-coupling of α-(acyloxy)-tri-n-butylstannanes with alkenyl, aryl, and heteroaryl electrophiles.

Racemic and scalemic α-(acyloxy)-tri-n-butylstannanes undergo Pd-catalyzed cross-couplings with alkenyl/aryl/heteroaryl iodides, bromides, and triflates in moderate to good yields in THF at 45 °C. Simple aryl iodides and unprotected aza-arenes, two classes of electrophiles that typically react sluggishly, are also good substrates. Cross-couplings proceed with retention of configuration at the alkenyl and stannyl-substituted stereocenters.

Synthesis of Enantioenriched α-(Hydroxyalkyl)-tri-n-butylstannanes†

A catalytically asymmetric synthesis of α-(hydroxyalkyl)-tri-n-butylstannanes 1 in good-excellent yields and enantioselectivities (up to 98% e.e.) via addition of ethyl(tri-n-butylstannyl)zinc to aldehydes was achieved. In practice, 1 was isolated after protection as its more stable ester or thiocarbamate (PG). The reagent was prepared from equimolar amounts of tri-n-butylstannyl hydride and Et2Zn in DME so as to avoid contamination by lithium and magnesium ions which suppress enantioselectivity.

Cascade Synthesis of (E)-2-Alkylidenecyclobutanols

A facile, one-pot reaction cascade condenses 1,1,1-trichloroalkanes with alpha,beta-unsaturated ketones to unexpectedly furnish moderate to good yields of (E)-2-alkylidenecyclobutanols.