Atroposelectivity in the electrophilic substitution reactions of laterally lithiated and silylated tertiary amides

Jonathan Clayden*, Jennifer H. Pink, Neil Westlund, Christopher S. Frampton

*Corresponding author for this work

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

26 Citations (Scopus)

Abstract

Lateral lithiation-electrophilic quench of 2-alkyl-1-naphthamides and 2,6-dialkylbenzamides yields products containing an atropisomeric Ar-CO axis and a new stereogenic centre with high (generally >95:5) diastereo-selectivity. With imines as electrophiles, single diastereoisomers containing an atropisomeric axis and two new stereogenic centres are formed. 2,6-Dialkylbenzamides may be functionalised stereoselectively at both the 2- and 6-positions, leading (with imines) to symmetrical compounds bearing 1,7-related stereogenic centres. 2-Alkylbenzamides with only one ortho alkyl group are not atropisomeric at ambient temperature but are functionalised diastereoselectively by lateral lithiation-electrophilic quench at - 78°C. Stabilisation of the atropisomeric products by further lithiation and alkylation proves their diastereoselective formation. The lack of stereospecificity in the fluoride-promoted reaction of a laterally silylated 1-naphthamide with an aldehyde suggests that reported reactions of laterally silylated benzamides may also be controlled by the rotationally restricted amide group.

Original languageEnglish
Pages (from-to)901-917
Number of pages17
JournalPerkin 1
Issue number7
DOIs
Publication statusPublished - 6 Mar 2002

Fingerprint

Dive into the research topics of 'Atroposelectivity in the electrophilic substitution reactions of laterally lithiated and silylated tertiary amides'. Together they form a unique fingerprint.

Cite this