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Rearrangement and Substitution of Pentadienyl Groups in Homopentadienylamines on Treatment with Organolithium Reagents
Author(s) -
Grilli Stefano,
Martelli Gianluca,
Savoia Diego
Publication year - 2001
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/1099-0690(200108)2001:15<2917::aid-ejoc2917>3.0.co;2-x
Subject(s) - chemistry , reagent , moiety , imine , amide , organolithium compounds , substitution (logic) , diamine , medicinal chemistry , stereochemistry , organic chemistry , catalysis , ion , computer science , deprotonation , programming language
(4 R ,5 R )‐ N , N′ ‐Bis[(1 S )‐1‐phenylethyl]‐3,6‐divinyl‐1,7‐octadiene‐4,5‐diamine underwent rearrangement and/or substitution of one/two pentadienyl groups on treatment with 2−4 equiv. of an organolithium reagent ( n BuLi, PhLi) in THF. By careful choice of experimental conditions, C 1 ‐ or C 2 ‐symmetric 1,2‐disubstituted 1,2‐diamines could generally be obtained with good stereocontrol. It is proposed that the reaction proceeds through competitive pathways involving a 1,3‐shift of the branched homopentadienyllithium amide moiety with retention of configuration and retro‐pentadienyllithiation to form an intermediate imine. In contrast, only rearrangement was observed on treatment of (1 R , S )‐ N ‐[(1 S )‐1‐phenylethyl]‐1‐(2‐pyridyl)‐2‐vinyl‐3‐butenylamine with 2 equiv. of n BuLi at −78 °C.