On the origins of kinetic resolution of cyclohexane-1,2-diols through stereoselective acylation by chiral tetrapeptides.
The relative energies of cyclohexane-1,2-diols and chiral tetrapeptide (2 (Boc) or 3 (Moc)) complexes calculated using DFT indicate a thermodynamic preference for chiral recognition toward (1R,2R)(e,e)-alpha isomer. The barrier for stereoselective acyl transfer is identified as lower for trans-(1R,2R)-cyclohexane-1,2-diol, leading to the kinetic resolution (KR) of trans-(1S,2S)-cyclohexane-1,2-diol. The prediction is in concert with the reported experiments for trans-diols, while that for hitherto unknown cis-diol demands experimental verification. It is proposed that desymmetrization would enable the resolution of cis-(1R,2S)-2-hydroxycyclohexyl acetate.
Shinisha
C B
CB
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
Sunoj
Raghavan B
RB
D000215:Acylation; D003511:Cyclohexanols / Q000737:chemistry*; D007700:Kinetics; D009842:Oligopeptides / Q000737:chemistry*; D013237:Stereoisomerism
D003511:Cyclohexanols; D009842:Oligopeptides; C064619:1,2-cyclohexanediol