Addition of Cl2C: to (−)-O-Menthyl Acrylate under Sonication−Phase-Transfer Catalysis. Efficient Synthesis of (+)- and (−)-(2-Chlorocyclopropyl)methanol
2005-05-13T00:00:00Z (GMT) by
Dichlorocyclopropanation of (−)-O-menthyl acrylate under conditions of phase-transfer catalysis (CHCl3, KOH, tetramethylammonium bromide), with sonication, gives excellent yields (85−94%) of the corresponding dichlorocyclopropanecarboxylate ester compared to thermal conditions (90 °C, 56%). No diastereoselectivity was observed, but one isomer was isolated pure by fractional crystallization. The measured kinetic isotope effect (initial rate (CHCl3)/rate (CDCl3) ∼1.7) suggests deprotonation of CHCl3 as the rate-limiting step.