F. Hammerschmidt, A. Hanninger
Nov 1, 1995
Citations
0
Influential Citations
28
Citations
Journal
Chemische Berichte
Abstract
Racemic and optically active 1-phenylethyl esters of pivalic, (—)-camphanic and 2,4,6-triisopropylbenzoic acid were prepared. The esters 7a of pivalic acid were deprotonated with lithium 2,2,6,6-tetramethylpiperidide (Li-TMP) to form α-oxy-α-methylbenzyllithium compounds which are partly con-figurationally stable prior to acylation with starting material. Camphanic ester (–)-7b cannot be deprotonated by Li-TMP and tBuLi is added to the ester function to afford ketone (–)-12a. 1-Phenylethyl 2,4,6-triisopropylbenzoates 16 were transformed within minutes to carbanions 19 by using sBuLi/TMEDA in THF, hexane, toluene and sBuLi without TMEDA in toluene/20% diethyl ether at –78°C. The carbanions are configurationally stable only in toluene/20% diethyl ether and racemise partly in the other solvents. They react with a variety of electrophiles with either retention [MeOD, AcOD, (MeO)2CO, CICO2Me] or inversion (Me3SnCl) of configuration. Carbanions 19 rearrange on warming to –20°C to hydroxy ketone 24 with racemisation.