Dual activation in asymmetric allylsilane addition to chiral N-acylhydrazones: method development, mechanistic studies, and elaboration of homoallylic amine adducts

Gregory K Friestad; Chandra Sekhar Korapala; Hui Ding

doi:10.1021/jo052037d

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Dual activation in asymmetric allylsilane addition to chiral N-acylhydrazones: method development, mechanistic studies, and elaboration of homoallylic amine adducts

Journal article

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Dual activation in asymmetric allylsilane addition to chiral N-acylhydrazones: method development, mechanistic studies, and elaboration of homoallylic amine adducts

Gregory K Friestad, Chandra Sekhar Korapala and Hui Ding

Journal of organic chemistry, Vol.71(1), pp.281-289

01/06/2006

DOI: 10.1021/jo052037d

PMID: 16388647

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Abstract

[reaction: see text] Chiral N-acylhydrazones derived from commercially available 4-benzyl-2-oxazolidinone provide a rigid, conformationally restricted template to impart facial selectivity in additions to C=N bonds. In the presence of indium(III) trifluoromethanesulfonate [In(OTf)3], N-acylhydrazones undergo highly diastereoselective fluoride-initiated additions of allylsilanes (aza-Sakurai reaction). Mechanistic studies including control experiments and comparisons with allyltributylstannane, allylmagnesium bromide, and allylindium species implicate a dual activation mechanism involving addition of an allylfluorosilicate species to a chelate formed from In(OTf)3 and the chiral N-acylhydrazone. The N-N bonds of the adducts are readily cleaved in a two-step protocol to provide synthetically useful homoallylic N-trifluoroacetamides. Further elaboration of the latter compounds through Wacker oxidation and olefin metathesis provides diversely functionalized building blocks and expands the potential applications of this C-C bond construction approach to asymmetric amine synthesis.

Amines - chemistry

Silanes - chemistry

Fluoroacetates

Magnetic Resonance Spectroscopy

Stereoisomerism

Hydrazones - chemistry

Alkenes - chemistry

Trifluoroacetic Acid - chemistry

Nitrogen - chemistry

Ketones - chemistry

Molecular Structure

Acetamides

Silicon - chemistry

Acylation

Aldehydes - chemistry

Electrons

Details

Title: Subtitle: Dual activation in asymmetric allylsilane addition to chiral N-acylhydrazones: method development, mechanistic studies, and elaboration of homoallylic amine adducts
Creators: Gregory K Friestad - Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, USA. gregory-friestad@uiowa.edu
Chandra Sekhar Korapala
Hui Ding
Resource Type: Journal article
Publication Details: Journal of organic chemistry, Vol.71(1), pp.281-289
DOI: 10.1021/jo052037d
PMID: 16388647
NLM abbreviation: J Org Chem
ISSN: 0022-3263
eISSN: 1520-6904
Publisher: United States
Grant note: GM-67187 / NIGMS NIH HHS
Language: English
Date published: 01/06/2006
Academic Unit: Chemistry
Record Identifier: 9983985974802771

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