Intramolecular [4 + 2] cycloadditions of iminoacetonitriles: a new class of azadienophiles for hetero Diels-Alder reactions.

Intramolecular [4 + 2] cycloadditions of iminoacetonitriles: a new class of azadienophiles for hetero Diels-Alder reactions. Research Abstract Details 

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Intramolecular [4 + 2] cycloadditions of iminoacetonitriles: a new class of azadienophiles for hetero Diels-Alder reactions. Abstract Text:

David T Amos,Adam R Renslo,Rick L Danheiser,

Iminoacetonitriles participate as reactive dienophiles in stereoselective intramolecular hetero Diels-Alder reactions which afford substituted quinolizidines. The cycloadduct with exo-oriented cyano group is obtained as the major or exclusive product of the reaction as a consequence of the alpha-amino nitrile anomeric effect The alpha-amino nitrile moieties incorporated in the cycloadducts constitute latent iminium ions, which upon exposure to mild protic or Lewis acids are unmasked, setting the stage for further useful synthetic transformations. For example, reductive decyanation with NaBH3CN excises the cyano group, while Bruylants reaction with Grignard reagents and acetylides lead to alpha-substituted amines. The substrates for these [4 + 2] cycloadditions are prepared from readily available alcohols via a Mitsunobu coupling reaction with the previously unknown, easily prepared reagent HN(Tf)CH2CN followed by cesium carbonate promoted elimination of trifluoromethanesulfinate.

Intramolecular [4 + 2] cycloadditions of iminoacetonitriles: a new class of azadienophiles for hetero Diels-Alder reactions. Publishing Authors By Initials

DT Amos,AR Renslo,RL Danheiser,

For similar organic chemicals: imines research abstracts see: organic chemicals: imines research

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Intramolecular [4 + 2] cycloadditions of iminoacetonitriles: a new class of azadienophiles for hetero Diels-Alder reactions. Journal Published:

PUBLICATION TYPE: Research Support, U.S. Gov't,

Journal: Journal of the American Chemical Society

VOLUME: 125

Page Numbers: 4970-1

Journal Abbreviation: J. Am. Chem. Soc.

ISSN: 0002-7863

DAY: 30

MONTH: Apr

YEAR: 2003

Intramolecular [4 + 2] cycloadditions of iminoacetonitriles: a new class of azadienophiles for hetero Diels-Alder reactions. Information

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LANGUAGE: eng

NlmUniqueID: 7503056

Intramolecular [4 + 2] cycloadditions of iminoacetonitriles: a new class of azadienophiles for hetero Diels-Alder reactions. Keywords Mesh Terms:

KEYWORDS: Imines

MESH TERMS: chemistry

Chemical & Substance for Abstract: Intramolecular [4 + 2] cycloadditions of iminoacetonitriles: a new class of azadienophiles for hetero Diels-Alder reactions. Information

Substance Name: Imines

Registry Number: 0

Grant and Affiliation Information for Intramolecular [4 + 2] cycloadditions of iminoacetonitriles: a new class of azadienophiles for hetero Diels-Alder reactions.

AFFILIATION: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.

Country: United States

AGENCY: United States NIGMS

GRANT: GM 28273

ACRONYM: GM

MEDLINETA: J Am Chem Soc

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