TY - JOUR
T1 - Kinetic resolution of α-acetoxy carboxylic acids with homochiral superQuats
AU - Bew, Sean P.
AU - Davies, Stephen G.
AU - Fukuzawa, Shin-Ichi
PY - 2000/1/1
Y1 - 2000/1/1
N2 - Preliminary investigations focused on the kinetic resolution of (±)-α- acetoxy mandelic carboxylic acid chloride with isopropyl SuperQuat and isopropyl Evans' homochiral auxiliaries. The addition of 2 equiv. of the acid chloride to the lithium salts of the auxiliaries (SuperQuat and Evans') at - 100°C in the THF afforded the corresponding N-acyl auxiliaries in high chemical yields (95% and 89%) and d.e.'s of 66% and 40%, respectively. Using the same mandelic acid chloride but incorporating SuperQuat auxiliaries derived from (S)-phenylglycine and (S)-phenylalanine yielded the corresponding N-acyl SuperQuats in 86% and 90% and d.e.'s of 66% and 30%, respectively. Substituting the phenyl group within the α-acetoxy mandelic acid chloride for a n-butyl, tert-butyl and cyclohexyl group changed the d.e. significantly when kinetically resolved with isopropyl SuperQuat. The yields were all similar, i.e., ~90% but the d.e.'s varied considerably, with values of 20%, 50%, and 82%, respectively. Attempted kinetic resolution of α- methoxyphenylacetyl chloride using the lithium salt of isopropyl SuperQuat revealed a diasteroselectivity of 45%, significantly lower than that obtained with the corresponding α-acetoxy carboxylic acid chlorides. (C) 2000 Wiley- Liss, Inc.
AB - Preliminary investigations focused on the kinetic resolution of (±)-α- acetoxy mandelic carboxylic acid chloride with isopropyl SuperQuat and isopropyl Evans' homochiral auxiliaries. The addition of 2 equiv. of the acid chloride to the lithium salts of the auxiliaries (SuperQuat and Evans') at - 100°C in the THF afforded the corresponding N-acyl auxiliaries in high chemical yields (95% and 89%) and d.e.'s of 66% and 40%, respectively. Using the same mandelic acid chloride but incorporating SuperQuat auxiliaries derived from (S)-phenylglycine and (S)-phenylalanine yielded the corresponding N-acyl SuperQuats in 86% and 90% and d.e.'s of 66% and 30%, respectively. Substituting the phenyl group within the α-acetoxy mandelic acid chloride for a n-butyl, tert-butyl and cyclohexyl group changed the d.e. significantly when kinetically resolved with isopropyl SuperQuat. The yields were all similar, i.e., ~90% but the d.e.'s varied considerably, with values of 20%, 50%, and 82%, respectively. Attempted kinetic resolution of α- methoxyphenylacetyl chloride using the lithium salt of isopropyl SuperQuat revealed a diasteroselectivity of 45%, significantly lower than that obtained with the corresponding α-acetoxy carboxylic acid chlorides. (C) 2000 Wiley- Liss, Inc.
UR - http://www.scopus.com/inward/record.url?scp=0034076832&partnerID=8YFLogxK
U2 - 10.1002/(SICI)1520-636X(2000)12:5/6<483::AID-CHIR33>3.0.CO;2-D
DO - 10.1002/(SICI)1520-636X(2000)12:5/6<483::AID-CHIR33>3.0.CO;2-D
M3 - Article
AN - SCOPUS:0034076832
SN - 0899-0042
VL - 12
SP - 483
EP - 487
JO - Chirality
JF - Chirality
IS - 5-6
ER -