Michael addition reactions between chiral equivalents of a nucleophilic glycine and (S)- or (R)-3-[(E)-enoyl]-4-phenyl-1,3-oxazolidin-2-ones as a general method for efficient preparation of beta-substituted pyroglutamic acids. Case of topographically controlled stereoselectivity.
This paper describes a systematic study of addition reactions between the chiral Ni(II) complex of the Schiff base of glycine with (S)-o-[N-(N-benzylprolyl)amino]benzophenone and (S)- or (R)-3-[(E)-enoyl]-4-phenyl-1,3-oxazolidin-2-ones as a general and synthetically efficient approach to beta-substituted pyroglutamic acids and relevant compounds. These reactions were shown to occur at room temperature in the presence of nonchelating organic bases and, most notably, with very high (>98% diastereomeric excess (de)) stereoselectivity at both newly formed stereogenic centers. The stereochemical outcome of the reactions was found to be overwhelmingly controlled by the stereochemical preferences of the Michael acceptors, and the chirality of the glycine complex influenced only the reaction rate. Thus, in the reactions of both the (S)-configured Ni(II) complex and the Michael acceptors, the reaction rates were exceptionally high, allowing preparation of the corresponding products with virtually quantitative (>98%) chemical and stereochemical yields. In contrast, reactions of the (S)-configured Ni(II) complex and (R)-configured Michael acceptors proceeded at noticeably lower rates, but the addition products were obtained in high diastereo- and enantiomeric purity. To rationalize the remarkably high and robust stereoselectivity observed in these reactions, we consider an enzyme-substrate-like mode of interaction involving a topographical match or mismatch of two geometric figures. Excellent chemical and stereochemical yields, combined with the simplicity and operational convenience of the experimental procedures, render the present method of immediate use for preparing various beta-substituted pyroglutamic acids and related compounds.
Soloshonok
Vadim A
VA
Department of Chemistry and Biochemistry, University of Oklahoma, Norman, Oklahoma 73019, USA. vadim@ou.edu
Cai
Chaozhong
C
Yamada
Takeshi
T
Ueki
Hisanori
H
Ohfune
Yasufumi
Y
Hruby
Victor J
VJ
D002384:Catalysis; D005998:Glycine / Q000737:chemistry*; D007700:Kinetics; D008956:Models, Chemical; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry*; D023303:Oxazolidinones / Q000737:chemistry*; D011761:Pyrrolidonecarboxylic Acid / Q000737:chemistry*; D012545:Schiff Bases / Q000737:chemistry; D016339:Spectrometry, Mass, Fast Atom Bombardment; D013237:Stereoisomerism
D023303:Oxazolidinones; D012545:Schiff Bases; D009532:Nickel; D011761:Pyrrolidonecarboxylic Acid; D005998:Glycine