Allylmetal-directed addition of 'O 2: Scope, mechanism and synthetic utility

Patrick H. Dussault, Charles T. Eary, Richard J. Lee, Umcsh R. Zope

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

Allylic silyl and stannyl groups strongly influence the regio- and stereochemistry of alkene oxygénations by 'O2, even within functionalized systems. Allylstannanes undergo anti-S E 2′ oxygenation to form both Z-stannylalkenyl hydroperoxides and 4-stannyl-1, 2-dioxolanes; the ene-like reaction is generally preferred unless limited by allylic strain. The alkenylstannane products, as well as the derived iodides, are effective substrates for palladium-mediated cross-couplings, additions, carbonylations, and acylations to form peroxydienes, peroxyenones, and peroxyenoates. Allylsilanes are less effective directing groups, possessing reactivity surprisingly similar to simple alkenes, and undergoing oxidation to form regioisomeric mixtures of hydroperoxides. The different reactivities and product distributions observed for allylstannanes and allylsilanes reflect different nucleophilicities of the ground state alkenes as well as variable polarization of the developing perepoxides by the neighboring C-Sn or C-Si bond. The observed selectivity for production of Z-alkenylmetals appears to result from the preferential formation of a single perepoxide pyramidal isomer and the tendency for this perepoxide to abstract the inside hydrogen on the metal-bearing carbon at a rate which is faster than either perepoxide inversion or single bond rotation to deliver the outside hydrogen for abstraction.

Original languageEnglish (US)
Pages (from-to)2189-2204
Number of pages16
JournalJournal of the Chemical Society - Perkin Transactions 1
Issue number15
DOIs
StatePublished - Jan 1 1999

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Alkenes
Hydrogen Peroxide
Hydrogen
Dioxolanes
Bearings (structural)
Carbonylation
Acylation
Stereochemistry
Oxygenation
Palladium
Iodides
Isomers
Ground state
Carbon
Metals
Polarization
Oxidation
Substrates
allylsilane

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Allylmetal-directed addition of 'O 2 : Scope, mechanism and synthetic utility. / Dussault, Patrick H.; Eary, Charles T.; Lee, Richard J.; Zope, Umcsh R.

In: Journal of the Chemical Society - Perkin Transactions 1, No. 15, 01.01.1999, p. 2189-2204.

Research output: Contribution to journalArticle

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