摘要:
The reaction of chiral vinyl sulfoxides with dichloroketene to yield optically active gamma-butyrolactones provides the basis for enantioselective syntheses of heterocyclic natural products. In particular, 2-alkylsulfinylindoles are transformed into butyrolactones that serve as precursors to the physostigmine alkaloids. The total synthesis of physostigmine in optically active form has revealed the importance of the size of alkyl group of the sulfoxide in the 3,3-sigmatropic rearrangement leading to the chiral butyrolactone. In addition, an efficient synthesis of optically active benzohydrofuran lactones which are precursors to the aflatoxins is described.
摘要:
The development of reagents for the asymmetric oxidation of sulfides to sulfoxides with high stereoselectivities is problematic because these substrates are nonfunctionalized. Nevertheless N-(phenylsulfonyl)(3,3-dichlorocamphoryl)oxaziridine (4) exhibits remarkably high and predictable ee's for the asymmetric oxidation of sulfides to sulfoxides (66->95% ee), selenides to selenoxides (90->95% ee) and sulfenimines to sulfinimines (85-91% ee). While steric effects are primarily responsible for the molecular recognition, an important electronic component is operational for those sulfides having an aryl group directly attached to the sulfur atom. The high ee's associate with this reagent are a consequence of the presence of complementary vacant regions and a molecular cleft or grove on the active site surface.