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Keywords:

  • chlorocyclization;
  • enantiodivergence;
  • enantioselectivity;
  • Eyring plots;
  • organocatalysis;
  • oxazolidinones

Abstract

A remarkable solvent-controlled enantiodivergence is seen in the hydroquinidine 1,4-phthalazinediyl diether ((DHQD)2PHAL)-catalyzed chlorocyclization of unsaturated carbamates. Eyring plot analyses of this previously unreported reaction are used to probe and compare the R- and S-selective pathways. In the CHCl3/hexanes solvent system, the pro-R process shows a surprising increase in selectivity with increasing temperature. These studies point to a strongly solvent-dependent entropy–enthalpy balance between the pro-R and pro-S pathways.