ISSN:
1434-193X
Keywords:
2,4,6-Triisopropylbenzoates, 1-indanyl, 1,2,3,4-tetrahydro-1-naphthyl
;
N,N-Diisopropylcarbamate, 1-indanyl
;
Carbanions, configurational sStability
;
Stereochemistry, stannylation
;
Liquid chromatography, determination of ee
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
2,4,6-Triisopropylbenzoates of 1-indanol and 1-tetralol (ee 98%) are deprotonated at -78 °C in hexane by sBuLi/TMEDA to give partly configurationally labile organolithium intermediates 5a and 5b, which are deuterated by MeOD with retention of configuration. These intermediates are stannylated by trimethyltin chloride with inversion as determined by lithiodestannylation followed by addition of MeOD to produce deuterated esters of low ee. Stannylation of (S)-5b with (-)-menthyldimethyltin bromide affords stannane 7 (de ≥ 95%) with inversion. The carbanion derived from (S)-1-indanyl N,N-diisopropylcarbamate (9) is configurationally stable. It reacts with trimethyltin chloride favouring inversion of configuration (ee up to 17%). Tributyltin chloride and tributyltin triflate yield stannanes 11b of opposite stereochemistry, the latter giving retention of configuration. Tributyltin bromide behaves similarly to the chloride, but the ee of the reaction product is only about 30%.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
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