Julian Priego

Sulfoxides as stereochemical controllers in intermolecular Heck reactions.

The study of a variety of substituted sulfoxides as chiral auxiliaries in intermolecular Heck reactions of sulfinyldihydrofurans and sulfinylcyclopentenes with different iodoarenes is reported. In the presence of [Pd(OAc)2]/Ag2CO3 and a bidentate phosphine ligand, synthetically useful yields and asymmetric inductions were obtained. By far the best diastereoselectivities were obtained by the use of the palladium-coordinating O-(N,N-dimethylamino)phenylsulfinyl group. By final removal of the chiral auxiliary, these sulfoxide-stereocontrolled asymmetric Heck processes were applied to the enantioselective synthesis of 1-aryl-substituted and 1,3-diaryl-substituted dihydrofurans and cyclopentenes.

STEREOSELECTIVE NUCLEOPHILIC EPOXIDATION OF HYDROXY VINYL SULFOXIDE DERIVATIVES

Abstract The diastereoselectivity of the nucleophilic epoxidation of vinyl sulfoxides bearing oxygenated substituents at allylic positions, 1–4, with MOO-t-Bu (M = Na, K) is primarily controlled by the chiral sulfur atom.

Aminosubstituted tert-butylsulfinylferrocenes as a new family of chiral ligands: asymmetric addition of diethylzinc to aldehydes

A ready access to a new family of planar chiral ferrocenes, the (RFc,RS)-2-amino substituted 1-tert-butylsulfinylferrocenes, is described; in the case of the sulfonamide series enantioselectivities of up to 96% were obtained in the addition of Et2Zn to aromatic aldehydes.

Highly stereoselective metal-catalyzed epoxidation of hydroxy vinyl sulfones 1

Acyclic α-hydroxyalkyl α,β-unsaturated sulfoxides undergo oxidation at sulfur followed by a highly regio- and stereoselective epoxidation at the electron deficient alkene by treatment with ButOOH–VO(acac)2; this methodology allows for an expedient entry into unusual carbohydrate fragments.