Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
17
pubmed:dateCreated
2003-4-23
pubmed:abstractText
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.
pubmed:grant
pubmed:commentsCorrections
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Apr
pubmed:issn
0002-7863
pubmed:author
pubmed:issnType
Print
pubmed:day
30
pubmed:volume
125
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
4970-1
pubmed:dateRevised
2011-9-26
pubmed:meshHeading
pubmed:year
2003
pubmed:articleTitle
Intramolecular [4 + 2] cycloadditions of iminoacetonitriles: a new class of azadienophiles for hetero Diels-Alder reactions.
pubmed:affiliation
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
pubmed:publicationType
Journal Article, Research Support, U.S. Gov't, P.H.S., Research Support, Non-U.S. Gov't