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

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

Access to Document

10.1016/j.steroids.2007.01.002

Cite this

@article{f39b132208a04349929efacc754b9236,

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.",

keywords = "Baeyer-Villiger reaction, Bile acids, Lactonization, Steroidal sapogenins",

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

year = "2007",

month = may,

day = "1",

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

language = "English",

volume = "72",

pages = "466--473",

journal = "Steroids",

issn = "0039-128X",

publisher = "Elsevier Inc.",

number = "5",

}

TY - JOUR

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

UR - http://www.scopus.com/inward/record.url?scp=34247156191&partnerID=8YFLogxK

U2 - 10.1016/j.steroids.2007.01.002

DO - 10.1016/j.steroids.2007.01.002

M3 - Article

C2 - 17412379

AN - SCOPUS:34247156191

SN - 0039-128X

VL - 72

SP - 466

EP - 473

JO - Steroids

JF - Steroids

IS - 5

ER -

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

Abstract

Keywords

Access to Document

Fingerprint

Cite this