Stereochemical course of the reductive spiroannulations of N-Boc and N-benzyl 2-cyanopiperidines

The stereochemical outcome of spiroannulations of N-protected 2-lithiopiperidines (generated by lithium di- tert-butyl biphenylide (LiDBB) mediated reductive lithiation of 2-cyanopiperidines) was investigated using deuterium labeled side-chains containing phosphate leaving groups. High stereoselecti...

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Bibliographic Details
Published inTetrahedron Vol. 61; no. 13; pp. 3371 - 3381
Main Authors Wolckenhauer, Scott A., Rychnovsky, Scott D.
Format Journal Article
LanguageEnglish
Published OXFORD Elsevier Ltd 28.03.2005
Elsevier
Subjects
Alkylation
Chemistry
Chemistry, Organic
Electrophilic addition
Lithiation
Physical Sciences
Science & Technology
Lithiation
Alkylation
Electrophilic addition
AMINONITRILES
LITHIOAMINE SYNTHETIC EQUIVALENTS
DISSOLVING METAL CONDITIONS
INTRAMOLECULAR CARBOLITHIATION
electrophilic addition
ALKYLLITHIUM
alkylation
ALPHA-AMINOORGANOLITHIUMS
lithiation
ANIONIC CYCLIZATIONS
PIPERIDINES
DIASTEREOISOMERS
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Summary:The stereochemical outcome of spiroannulations of N-protected 2-lithiopiperidines (generated by lithium di- tert-butyl biphenylide (LiDBB) mediated reductive lithiation of 2-cyanopiperidines) was investigated using deuterium labeled side-chains containing phosphate leaving groups. High stereoselectivity was observed when benzyl (Bn) protected 2-cyanopiperidines were employed, while tert-butoxycarbonyl (Boc) protected 2-cyanopiperidines afforded lower selectivity. Models are proposed to rationalize the results of this study. Graphical Abstract
ISSN:0040-4020
1464-5416
DOI:10.1016/j.tet.2005.01.099