Virtually complete control of simple and face diastereoselectivity in the Michael addition reactions between achiral equivalents of a nucleophilic glycine and (S)- or (R)-3-(E-enoyl)-4-phenyl-1,3-oxazolidin-2-ones: practical method for preparation of beta-substituted pyroglutamic acids and prolines.
This study demonstrates a new strategy for controlling the stereochemical outcome of the Michael addition reactions between nucleophilic glycine equivalents and alpha,beta-unsaturated carboxylic acid derivatives: The addition reactions between achiral Ni(II)-complex of the Schiff base of glycine with o-[N-alpha-pycolylamino]acetophenone and (S)- or (R)-3-(E-enoyl)-4-phenyl-1,3-oxazolidin-2-ones were shown to occur at room temperature in the presence of nonchelating organic bases and, most notably, with very high stereoselectivity at both newly formed stereogenic centers. Thus, the chiral 4-phenyl-1,3-oxazolidin-2-one moiety was found to control efficiently both face diastereoselectivities of the glycine derived enolate and the C,C double bond of the Michael acceptor. The new strategy developed in this work is methodologically superior to previous methods, most notably in terms of generality and synthetic efficiency. Excellent chemical yields and diastereoselectivities, combined with the simplicity of the experimental procedures, render the present method of immediate use for preparing various 3-substituted pyroglutamic acids and related amino acids (glutamic acids, glutamines, prolines, etc.) available via conventional transformations of the former.
Soloshonok
Vadim A
VA
Department of Chemistry and Biochemistry, University of Oklahoma, Norman, OK 73019, USA.
Ueki
Hisanori
H
Tiwari
Rohit
R
Cai
Chaozhong
C
Hruby
Victor J
VJ
D005998:Glycine / Q000737:chemistry*; D015394:Molecular Structure; D011392:Proline / Q000138:chemical synthesis* / Q000737:chemistry; D011761:Pyrrolidonecarboxylic Acid / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
D011392:Proline; D011761:Pyrrolidonecarboxylic Acid; D005998:Glycine