Rational design of highly diastereoselective, organic base-catalyzed, room-temperature Michael addition reactions.
Via the rational design of a single-preferred transition state, stabilized by electron donor-acceptor-type attractive interactions, structural and geometric requirements for the corresponding starting compounds have been determined. The Ni(II) complex of the Schiff base of glycine with o-[N-alpha-picolylamino]acetophenone, as a nucleophilic glycine equivalent, and N-(trans-enoyl)oxazolidin-2-ones, as derivatives of an alpha,beta-unsaturated carboxylic acid, were found to be the substrates of choice featuring geometric/conformational homogeneity and high reactivity. The corresponding Michael addition reactions were found to proceed at room temperature in the presence of catalytic amounts of DBU to afford quantitatively the addition products with virtually complete diastereoselectivity. Acidic decomposition of the products followed by treatment of the reaction mixture with NH4OH gave rise to the diastereomerically pure 3-substituted pyroglutamic acids.
Soloshonok
V A
VA
Department of Chemistry, University of Arizona, Tucson 85721, USA.
Cai
C
C
Hruby
V J
VJ
Van Meervelt
L
L
Yamazaki
T
T
D002384:Catalysis; D004583:Electrons; D005998:Glycine / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D011761:Pyrrolidonecarboxylic Acid / Q000031:analogs & derivatives* / Q000138:chemical synthesis*; D012545:Schiff Bases / Q000737:chemistry*; D013237:Stereoisomerism; D014961:X-Ray Diffraction
D012545:Schiff Bases; D011761:Pyrrolidonecarboxylic Acid; D005998:Glycine