The Prins cyclization of hydroxy or amino group-containing allenylsilanes with carbonyl compounds occurred at the allenic terminus in a regio- and stereoselective manner to give the di- or trisubstituted tetrahydrofurans, tetrahydropyrans, and pyrrolidines. During the reaction, the allenic axial chirality of the starting material was efficiently transferred to the newly formed carbon chiral centers of the product.

The highly diastereoselective synthesis of the marine natural product, (−)-manzacidin B, is described. A novel copper-catalyzed aldol reaction of the α-methylserine-derived aldehyde with an isocyanoacetate possessing (1R)-camphorsultam as the chiral auxiliary proceeded in a highly diastereoselective manner to give the (4R,5R,6R)-adduct, which was converted into manzacidin B in a few steps.

A highly diastereoselective total synthesis of (−)-kaitocephalin, a novel antagonist of ionotropic glutamate receptors, was accomplished in 12 steps starting from 5-substituted proline ester via the aldol reaction with OBO-serine aldehyde, (E)-selective α,β-dehydroamino acid synthesis using a new HWE reagent, and catalytic hydrogenation.

The functionalized pyroglutamate core unit, (2R,4R)-3, which could be converted into the β-lactone/pyrrolidine or γ-lactone/pyrrolidine ring system of oxazolomycin A 1 and neooxazolomycin 2, and which possesses an exomethylene group at C3 as a scaffold for the construction of their C3 polyene segment, was synthesized by the Michael reaction of a glycine Schiff base 4 with the α,β-disubstituted acrylate 8 as the key step.(R)-3-((E)-4-(Benzyloxy)but-2-enoyl)-4-phenyloxazolidin-2-oneC20H19NO4[α]D20.9=-69.9 (c 1.07, CHCl3)Source of chirality: (R)-α-phenylglycineAbsolute configuration: (R)(2R,3R)-Methyl 3-((benzyloxy)methyl)-5-oxopyrrolidine-2-carboxylateC14H17NO4[α]D27.0=-27.3 (c 1.0, CHCl3)Source of chirality: (R)-α-phenylglycineAbsolute configuration: (2R,3R)(S)-3-((E)-4-(Benzyloxy)-2-methylbut-2-enoyl)-4-phenyloxazolidin-2-oneC21H21NO4[α]D20.5=+12.9 (c 0.77, CHCl3)Source of chirality: (R)-α-phenylglycineAbsolute configuration: (S)N-(2-Benzoyl-phenyl)-2-piperidyl-acetamide Ni(II) complex of (2S,3S,4R,4′S)-3-benzyloxymethyl-4-methyl-5-[3′-(4′-phenyl-2′-oxazolidinonyl)] glutamic acid schiff baseC43H44N4O7Ni[α]D21.2=+2376.3 (c 0.4, CHCl3)Source of chirality: (S)-4-phenyloxazolidin-2-oneAbsolute configuration: (2S,3S,4R,4′S)(2S,3S,4R)-3-((Benzyloxy)methyl)-4-methyl-5-oxopyrrolidine-2-carboxylic acidC14H17NO4[α]D25.7=+24.3 (c 1.0, CHCl3)Source of chirality: (–)-verbenone and stereoselective synthesisAbsolute configuration: (2S,3S,4R)(2S,3S,4R)-tert-Butyl 3-((benzyloxy)methyl)-4-methyl-5-oxopyrrolidine-2-carboxylateC18H25NO4[α]D25.4=+14.9 (c 1.4, CHCl3)Source of chirality: (–)-verbenone and stereoselective synthesisAbsolute configuration: (2S,3S,4R)(2S,3S,4R)-tert-Butyl-3-((benzyloxy)methyl)-1,4-dimethyl-5-oxopyrrolidine-2-carboxylateC19H27NO4[α]D26.1=+25.8 (c 1.1, CHCl3)Source of chirality: (–)-verbenone and stereoselective synthesisAbsolute configuration: (2S,3S,4R)((2S,3S,4R)-2-(tert-Butoxycarbonyl)-1,4-dimethyl-5-oxopyrrolidin-3-yl)methyl methyl carbonateC14H23NO6[α]D27.0=+27.5 (c 3.4, CHCl3)Absolute configuration: (2S,3S,4R)(3R,3aS,6aR)-tert-Butyl-hexahydro-1,3-dimethyl-2,6-dioxo-1H-furo[3,4-b]pyrrole-6a-carboxylateC13H19NO5[α]D25.1=+88.7 (c 1.8, CHCl3)Absolute configuration: (3R,3aS,6aR)(2R,3S,4R)-2-tert-butyl 2-methyl 1,4-dimethyl-5-oxo-3-((phenylselanyl)methyl) pyrrolidine-2,2-dicarboxylateC20H27NO5Se[α]D26.7=-52.8 (c 0.9, CHCl3)Absolute configuration: (2R,3S,4R)(2R,4R)-2-tert-Butyl 2-methyl 1,4-dimethyl-3-methylene-5-oxopyrrolidine-2,2-dicarboxylateC14H21NO5[α]D25=-84.0 (c 1.3, CHCl3)Absolute configuration: (2R,4R)(2R,4R)-tert-Butyl 2-(hydroxymethyl)-1,4-dimethyl-3-methylene-5-oxopyrrolidine-2-carboxylateC13H21NO4[α]D25=-85.7 (c 1.2, CHCl3)Absolute configuration: (2R,3S,4R)