Metal-free dihydroxylation of alkenes using cyclobutane malonoyl peroxide

Nick Tomkinson, Kevin M Jones

Research output: Contribution to journalArticle

42 Citations (Scopus)

Abstract

Cyclobutane malonoyl peroxide (7), prepared in a single step from the commercially available diacid 6, is an effective reagent for the dihydroxylation of alkenes. Reaction of a chloroform solution of 7 with an alkene in the presence of one equivalent of water at 40 °C followed by alkaline hydrolysis leads to the corresponding diol (30–84%). With 1,2-disubstituted alkenes the reaction proceeds with syn-selectivity (3:1–>50:1). A mechanism consistent with experimental findings is proposed which is supported by deuterium and oxygen labeling studies and explains the stereoselectivity observed. Alternative reaction pathways that are dependent on the structure of the starting alkene are also described leading to the synthesis of allylic alcohols and γ-lactones.
LanguageEnglish
Pages921-928
Number of pages8
JournalJournal of Organic Chemistry
Volume77
Issue number2
DOIs
Publication statusPublished - Jan 2012

Fingerprint

Cyclobutanes
Peroxides
Alkenes
Metals
Stereoselectivity
Deuterium
Lactones
Chloroform
Labeling
Hydrolysis
Oxygen
Water

Keywords

  • dihydroxylation
  • alkenes
  • cyclobutane malonoyl peroxide

Cite this

@article{d2d3a9fa5dc34e13bc2f74184a3d0ffd,
title = "Metal-free dihydroxylation of alkenes using cyclobutane malonoyl peroxide",
abstract = "Cyclobutane malonoyl peroxide (7), prepared in a single step from the commercially available diacid 6, is an effective reagent for the dihydroxylation of alkenes. Reaction of a chloroform solution of 7 with an alkene in the presence of one equivalent of water at 40 °C followed by alkaline hydrolysis leads to the corresponding diol (30–84{\%}). With 1,2-disubstituted alkenes the reaction proceeds with syn-selectivity (3:1–>50:1). A mechanism consistent with experimental findings is proposed which is supported by deuterium and oxygen labeling studies and explains the stereoselectivity observed. Alternative reaction pathways that are dependent on the structure of the starting alkene are also described leading to the synthesis of allylic alcohols and γ-lactones.",
keywords = "dihydroxylation , alkenes, cyclobutane malonoyl peroxide",
author = "Nick Tomkinson and Jones, {Kevin M}",
year = "2012",
month = "1",
doi = "10.1021/jo202084w",
language = "English",
volume = "77",
pages = "921--928",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "2",

}

Metal-free dihydroxylation of alkenes using cyclobutane malonoyl peroxide. / Tomkinson, Nick; Jones, Kevin M.

In: Journal of Organic Chemistry, Vol. 77, No. 2, 01.2012, p. 921-928.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Metal-free dihydroxylation of alkenes using cyclobutane malonoyl peroxide

AU - Tomkinson, Nick

AU - Jones, Kevin M

PY - 2012/1

Y1 - 2012/1

N2 - Cyclobutane malonoyl peroxide (7), prepared in a single step from the commercially available diacid 6, is an effective reagent for the dihydroxylation of alkenes. Reaction of a chloroform solution of 7 with an alkene in the presence of one equivalent of water at 40 °C followed by alkaline hydrolysis leads to the corresponding diol (30–84%). With 1,2-disubstituted alkenes the reaction proceeds with syn-selectivity (3:1–>50:1). A mechanism consistent with experimental findings is proposed which is supported by deuterium and oxygen labeling studies and explains the stereoselectivity observed. Alternative reaction pathways that are dependent on the structure of the starting alkene are also described leading to the synthesis of allylic alcohols and γ-lactones.

AB - Cyclobutane malonoyl peroxide (7), prepared in a single step from the commercially available diacid 6, is an effective reagent for the dihydroxylation of alkenes. Reaction of a chloroform solution of 7 with an alkene in the presence of one equivalent of water at 40 °C followed by alkaline hydrolysis leads to the corresponding diol (30–84%). With 1,2-disubstituted alkenes the reaction proceeds with syn-selectivity (3:1–>50:1). A mechanism consistent with experimental findings is proposed which is supported by deuterium and oxygen labeling studies and explains the stereoselectivity observed. Alternative reaction pathways that are dependent on the structure of the starting alkene are also described leading to the synthesis of allylic alcohols and γ-lactones.

KW - dihydroxylation

KW - alkenes

KW - cyclobutane malonoyl peroxide

UR - http://www.scopus.com/inward/record.url?scp=84856116141&partnerID=8YFLogxK

U2 - 10.1021/jo202084w

DO - 10.1021/jo202084w

M3 - Article

VL - 77

SP - 921

EP - 928

JO - Journal of Organic Chemistry

T2 - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 2

ER -