(Diene)Rh(I) complexes catalyze the stereoselective three-component coupling of silyl glyoxylates, arylboronic acids, and aldehydes to give glycolate aldol products. The participation of Rh-alkoxides in the requisite Brook rearrangement was established through two component Rh-catalyzed couplings of silyl glyoxylates with ArB(OH) to give silyl-protected mandelate derivatives. The intermediacy of a chiral Rh-enolate was inferred through enantioselective protonation using a chiral Rh-catalyst.
View Article and Find Full Text PDFAn efficient synthesis of chiral nonracemic diene ligands is facilitated by an enantioselective dearomative intermolecular arene cyclopropanation of anisole. The functionality of the resulting cycloheptatriene engenders distinct chemical environments in a downstream tricyclic bis(enol) triflate that permits selective late-stage functionalization. The synthesis of diverse - and --symmetric dienes is therefore viable by iterative palladium-catalyzed cross-coupling reactions.
View Article and Find Full Text PDFArene cyclopropanation offers a direct route to higher-order, non-aromatic carbocycles; however, the inherent issue of dictating site selectivity has cumbered the development of novel intermolecular reactions that directly engage the arene pool. This paper describes a highly regio- and stereoselective, Rh[()-PTTL]-catalyzed arene cyclopropanation using α-cyanodiazoacetates to afford stable norcaradienes bearing three stereogenic centers, one of which is an all-carbon quaternary center. The enantioenriched norcaradienes served as tunable templates for further transformation into stereochemically dense, fused and bicyclic carbocycles containing transmutable functionality.
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