Diastereoselective ortholithiation and conformational control in stereospecific dearomatising anionic cyclisations

Ryan A. Bragg, Jonathan Clayden*

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

26 Citations (Scopus)

Abstract

The dearomatising anionic cyclisation of tertiary naphthamides bearing chiral N-substituents (such as α-methylbenzyl) is stereospecific and retentive not because of a configurationally stable organolithium intermediate but because the starting material exists as two atropisomers at -78°C, of which only one is lithiated. The initially formed ortholithiated amide can be trapped with MeI to give single diastereoisomers of atropisomeric amides bearing chiral N-substituents. Given time, even in the absence of DMPU, the ortholithiated amide undergoes anion translocation to an α-lithiated species, which can cyclise only to one diastereoisomer of the product, leading to the observed stereospecificity.

Original languageEnglish
Pages (from-to)8327-8331
Number of pages5
JournalTetrahedron Letters
Volume40
Issue number48
DOIs
Publication statusPublished - 26 Nov 1999

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