Asymmetric Epoxidation of Allylic Alcohols: the Katsuki–Sharpless Epoxidation Reaction

Abstract

In 1980, Sharpless and Katsuki discovered a system for the asymmetric epoxidation of primary allylic alcohols that utilizes Ti(OPr‐ i ) 4 , a dialkyl tartrate as a chiral ligand, and tert ‐butyl hydroperoxide as the oxidant. Notably, this reaction exhibits high levels of enantioselectivity (usually > 90% ee). Like other metal‐catalyzed epoxidations, this reaction also proceeds under mild conditions with good chemical yield and with high regio‐ and chemoselectivity. Various aspects of this reaction, including its mechanism, early synthetic applications, and further transformations of the epoxy alcohol product, have been reviewed. In this chapter, the full scope and limitations of this reaction, its synthetic applications, and typical experimental conditions are described.

Metal–organic frameworks as heterogeneous catalysts for oxidation reactions

“…89 It is worth commenting that chiral epoxidations of allylic alcohols reported by Sharpless using homogeneous chiral titanium complexes as catalysts constituted a milestone in this area. 90 As an example of how chiral MOFs can be used as catalysts for alkene epoxidation, Nguyen and coworkers studied the The reader is referred to recent reviews 33 on chiral MOFs for a more complete coverage on this topic but for the present purpose, we should stress that a methodology in which molecular oxygen or organic hydroperoxides are the final oxidants and some chiral cocatalysts is used in small percentages is still to be developed and will be significant development in the field of catalytic enantioselective oxidations.…”

Chemistry, Biology, and Medicine of the Glycopeptide Antibiotics

“…Scheme 5. Synthesis of AA-4 derivative (R)-33 of vancomycin through enzymatic resolution according to Zhu et al [114] The catalytic asymmetric epoxidation (AE) of allylic alcohols, [115] the asymmetric dihydroxylation (AD) of olefins [116] and the asymmetric aminohydroxylation (AA) of olefins, [117] all developed by the Sharpless group, have been applied productively to the synthesis of aryl glycines as shown in Schemes 6, [118] 7, [119] and 8, [120] respectively. [119,120] The electrophilic amination of oxazolidinone derived enolates was developed by the Evans group in the late 1980s.…”

Chemie, Biologie und medizinische Anwendungen der Glycopeptid-Antibiotika

“…Die katalytische asymmetrische Epoxidierung (AE) von Allylalkoholen, [115] die asymmetrische Dihydroxylierung (AD) von Olefinen [116] und die asymmetrische Aminohydroxylierung (AA) von Olefinen [117] ± Reaktionen, die von Sharpless et al entwickelt wurden ± wurden alle produktiv für die Synthese von Arylglycinen genutzt, wie in Schema 6 [118] , 7 [119] und 8 [120] [116] ).…”