Phosphine-catalyzed reductions of alkyl silyl peroxides by titanium hydride reducing agents

Development of the method and mechanistic investigations

Jason R. Harris, M. Taylor Haynes, Andrew M. Thomas, Keith Woerpel

Research output: Contribution to journalArticle

Abstract

(Figure presented) A method that allows for the reduction of protected hydroperoxides by employing catalytic amounts of phosphine is presented. The combination of a titanium(IV) alkoxide and a siloxane allowed for the chemoselective reduction of phosphine oxides in the presence of alkyl silyl peroxides. Subsequent reduction of the peroxide moiety by phosphine provided the corresponding silylated alcohols in useful yields. Mechanistic experiments, including crossover experiments, support a mechanism in which the peroxide group was reduced and the silyl group was transferred in a concerted step. Labeling studies with 17O-labeled peroxides demonstrate that the oxygen atom adjacent to the silicon atom is removed from the silyl peroxide.

Original languageEnglish (US)
Pages (from-to)5083-5091
Number of pages9
JournalJournal of Organic Chemistry
Volume75
Issue number15
DOIs
StatePublished - Aug 6 2010

Fingerprint

phosphine
Reducing Agents
Peroxides
Titanium
Hydrides
Siloxanes
Atoms
Silicon
Oxides
Labeling
Hydrogen Peroxide
Experiments
Alcohols
Oxygen

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Phosphine-catalyzed reductions of alkyl silyl peroxides by titanium hydride reducing agents : Development of the method and mechanistic investigations. / Harris, Jason R.; Haynes, M. Taylor; Thomas, Andrew M.; Woerpel, Keith.

In: Journal of Organic Chemistry, Vol. 75, No. 15, 06.08.2010, p. 5083-5091.

Research output: Contribution to journalArticle

@article{46ec691431e84d06a8c9e9ca3f16d269,
title = "Phosphine-catalyzed reductions of alkyl silyl peroxides by titanium hydride reducing agents: Development of the method and mechanistic investigations",
abstract = "(Figure presented) A method that allows for the reduction of protected hydroperoxides by employing catalytic amounts of phosphine is presented. The combination of a titanium(IV) alkoxide and a siloxane allowed for the chemoselective reduction of phosphine oxides in the presence of alkyl silyl peroxides. Subsequent reduction of the peroxide moiety by phosphine provided the corresponding silylated alcohols in useful yields. Mechanistic experiments, including crossover experiments, support a mechanism in which the peroxide group was reduced and the silyl group was transferred in a concerted step. Labeling studies with 17O-labeled peroxides demonstrate that the oxygen atom adjacent to the silicon atom is removed from the silyl peroxide.",
author = "Harris, {Jason R.} and Haynes, {M. Taylor} and Thomas, {Andrew M.} and Keith Woerpel",
year = "2010",
month = "8",
day = "6",
doi = "10.1021/jo1008367",
language = "English (US)",
volume = "75",
pages = "5083--5091",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "15",

}

TY - JOUR

T1 - Phosphine-catalyzed reductions of alkyl silyl peroxides by titanium hydride reducing agents

T2 - Development of the method and mechanistic investigations

AU - Harris, Jason R.

AU - Haynes, M. Taylor

AU - Thomas, Andrew M.

AU - Woerpel, Keith

PY - 2010/8/6

Y1 - 2010/8/6

N2 - (Figure presented) A method that allows for the reduction of protected hydroperoxides by employing catalytic amounts of phosphine is presented. The combination of a titanium(IV) alkoxide and a siloxane allowed for the chemoselective reduction of phosphine oxides in the presence of alkyl silyl peroxides. Subsequent reduction of the peroxide moiety by phosphine provided the corresponding silylated alcohols in useful yields. Mechanistic experiments, including crossover experiments, support a mechanism in which the peroxide group was reduced and the silyl group was transferred in a concerted step. Labeling studies with 17O-labeled peroxides demonstrate that the oxygen atom adjacent to the silicon atom is removed from the silyl peroxide.

AB - (Figure presented) A method that allows for the reduction of protected hydroperoxides by employing catalytic amounts of phosphine is presented. The combination of a titanium(IV) alkoxide and a siloxane allowed for the chemoselective reduction of phosphine oxides in the presence of alkyl silyl peroxides. Subsequent reduction of the peroxide moiety by phosphine provided the corresponding silylated alcohols in useful yields. Mechanistic experiments, including crossover experiments, support a mechanism in which the peroxide group was reduced and the silyl group was transferred in a concerted step. Labeling studies with 17O-labeled peroxides demonstrate that the oxygen atom adjacent to the silicon atom is removed from the silyl peroxide.

UR - http://www.scopus.com/inward/record.url?scp=77955157299&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=77955157299&partnerID=8YFLogxK

U2 - 10.1021/jo1008367

DO - 10.1021/jo1008367

M3 - Article

VL - 75

SP - 5083

EP - 5091

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 15

ER -