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

Daniel G. Rivera; Orlando Pando; Reynier Suardiaz; Francisco Coll

doi:10.1016/j.steroids.2007.01.002

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

Daniel G. Rivera^*, Orlando Pando, Reynier Suardiaz, Francisco Coll

^*Corresponding author for this work

School of Biological Sciences

Research output: Contribution to journal › Article › peer-review

Abstract

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.

Original language	English
Pages (from-to)	466-473
Number of pages	8
Journal	Steroids
Volume	72
Issue number	5
DOIs	https://doi.org/10.1016/j.steroids.2007.01.002
Publication status	Published - 1 May 2007

Keywords

Baeyer-Villiger reaction
Bile acids
Lactonization
Steroidal sapogenins

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10.1016/j.steroids.2007.01.002

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

abstract = "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.",

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author = "Rivera, {Daniel G.} and Orlando Pando and Reynier Suardiaz and Francisco Coll",

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doi = "10.1016/j.steroids.2007.01.002",

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T1 - Studies on the regioselectivity of the Baeyer-Villiger reaction of 3-keto steroids

T2 - conformational effects determine the migration aptitude

AU - Rivera, Daniel G.

AU - Pando, Orlando

AU - Suardiaz, Reynier

AU - Coll, Francisco

PY - 2007/5/1

Y1 - 2007/5/1

N2 - 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.

AB - 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.

KW - Baeyer-Villiger reaction

KW - Bile acids

KW - Lactonization

KW - Steroidal sapogenins

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U2 - 10.1016/j.steroids.2007.01.002

DO - 10.1016/j.steroids.2007.01.002

M3 - Article

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AN - SCOPUS:34247156191

VL - 72

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EP - 473

JO - Steroids

JF - Steroids

SN - 0039-128X

IS - 5

ER -

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

Abstract

Keywords

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