M. Bilodeau. D.A. Evans A Survey of Soft Enolization Techniques Chem 115 Lithium halide enolizations Magnesium Enolates Kelleher, McKervey, Vibuljan Chem Comm. 1980, 486-488 1986.16.1133-1139 Diethylmalonate acylation C.1 R= n-CBH11, 85% CI MeCN. rt TMSCL, Et3N 85% yield Et20, reflux Reaction can be brought about with less than 1 equiv of Lil. COOH Kaiser. Fohlisch He/. Chim. Acta. 1990. 73. 1504-1514 70% yield 人 MgCh, 2 equiv Et3N, 4 equiv EtOH 75% yield Evans, Bilodeau unpublished results Harmata. Elahmad Tetrahedron lett. 1993. 34. 789-792 MgBr2.0Et2 3M LICIO4 Et2O 16: 1 ratio of isomers Deuterium quench indicates 25% enolization of N-propionyloxazolidinone 22A-04 Ketone Acidity 11/1/01 3: 42 PMRathke M. Bilodeau, D.A. Evans A Survey of 'Soft' Enolization Techniques Chem 115 16:1 ratio of isomers 3M LiClO4 Et3N Et2O Harmata, Elahmad Tetrahedron Lett. 1993, 34, 789-792. 70% yield + LiClO4 Et3N Et2O Kaiser, Fohlisch Helv. Chim. Acta. 1990, 73, 1504-1514. "Reaction can be brought about with less than 1 equiv of LiI." 76%, 60:40 ratio of diastereomers LiI TMSCl, Et3N Et2O, reflux PhCHO R= Ph, 77% R= n-C6H11, 85% slow addn of: RCHO Et2O reflux 4 equiv + LiI 1 equiv Lithium Halide Enolizations Kelleher, McKervey, Vibuljan Chem. Comm. 1980, 486-488. - Evans, Bilodeau unpublished results. 73% yield, 93:7 diastereomer ratio Magnesium Enolates Deuterium quench indicates 25% enolization of N-propionyloxazolidinone MgBr2•OEt2 Et3N CH2Cl2, 0° C 75% yield MVK EtOH MgCl2, 2 equiv Et3N, 4 equiv CO2 MeCN rt 70 % yield MgCl2, 2 equiv NaI, 2 equiv Et3N, 4 equiv CO2 MeCN rt Ketone Carboxylation 85% yield MgCl2, 1 equiv Et3N, 2 equiv MeCN, rt Diethylmalonate acylations J. Org. Chem. 1985, 50, 2622-2624. J. Org. Chem. 1985, 50, 4877-4879. Syn. Comm. 1986, 16, 1133-1139. Me O Me Me O R Me O Me Me O Me Ph OH O O Cl Cl Cl O O O O Cl O O Cl O O O EtO O OEt Me O Cl OEt O EtO O O Me O O COOH O O O O Mg O Me O O N Bn O Me O CO2Me O Me N O Bn O CO2Me 22A-04 Ketone Acidity 11/1/01 3:42 PM