Studies on the regioselectivity of the Baeyer-Villiger reaction of 3-keto steroids: conformational effects determine the migration aptitude

Autor:	Orlando Pando, Reynier Suardíaz, Francisco Coll, Daniel G. Rivera
Rok vydání:	2006
Předmět:	Pharmacology Molecular Structure Chemistry Stereochemistry medicine.medical_treatment Organic Chemistry Clinical Biochemistry Regioselectivity Criegee rearrangement Biochemistry Steroid Endocrinology medicine Steroids Molecular Biology Oxidation-Reduction
Zdroj:	Steroids. 72(5)
ISSN:	0039-128X
Popis:	A detailed study of the Baeyer-Villiger reaction of 3-ketosteroids has been performed by using m -chloroperoxybenzoic and trifluoroperoxyacetic acids as oxidants. The process was fully regiospecific for 3-keto-5α-steroids with the employ of both peracids, and only partially regioselective for 3-keto-5β-steroids by using trifluoroperoxyacetic acid. Interestingly, the reaction resulted completely unselective for 3-keto-5β-steroids by using m -chloroperoxybenzoic acid. Theoretical studies were performed to explain the regiochemistry of this process, which is suggested to be controlled by conformational effects in the transition state of the Criegee rearrangement.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::56b05fc5596106ecac1bc207637260c7 https://pubmed.ncbi.nlm.nih.gov/17412379 Zobrazit plný text záznamu Full Text from ScienceDirect