Diastereoselective synthesis of aryl and alkyl trans-glycidic amides from pseudoephedrine-derived sulfonium salt. Chemospecific exo-tet ring closure for morpholin-3-ones

• Published in: Tetrahedron Vol. 68; no. 49; pp. 10252 - 10256
• Main Authors: Aparicio, David M., Gnecco, Dino, Juárez, Jorge R., Orea, María L., Mendoza, Angel, Waksman, Noemí, Salazar, Ricardo, Fores-Alamo, Marcos, Terán, Joel L.
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 09.12.2012; Elsevier
• Subjects: 6-exo-tet Ring closure; Amides; Aromatic compounds; Chemistry; Chemistry, Organic; Chemospecific; Closures; Diastereoselective; Epoxidation; Exact sciences and technology; Fragmentation; Heterocyclic compounds; Heterocyclic compounds with n hetero atom and also o and/or s, se, te hetero atoms; Morpholin-3-ones; Organic chemistry; Physical Sciences; Precursors; Preparations and properties; Science & Technology; Synthesis; Tetrahedrons; trans-Glycidic amides; Morpholin-3-ones; Diastereoselective; Chemospecific; trans-Glycidic amides; 6-exo-tet Ring closure; ASYMMETRIC-SYNTHESIS; ACIDS; ENANTIOSELECTIVE DARZENS REACTION; ALDEHYDES; EPOXIDATION; STABILIZED SULFUR YLIDES; PRACTICAL CHIRAL AUXILIARY; CONDENSATION; STEREOSELECTIVE-SYNTHESIS; STEREOCONTROLLED SYNTHESIS; Organic cation; Exo stereoisomer; Chiral compound; Selectivity; Stereochemistry; Morpholine derivatives; Regiospecificity; Diastereoselectivity; Alkaloid; Pseudoephedrine; Cyclization; Functionalization; Epoxidation; Carboxamide; Aromatic compound; Chemical synthesis; Sulfonium compound; Oxygen nitrogen heterocycle
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/j.tet.2012.09.047

A regiospecific and high diastereoselective synthesis of trans-glycidic amides coming from a common pseudoephedrine sulfonium salt 2 precursor is presented. This is the first example in where the diastereoselectivity is controlled by a chiral noncyclic amide fragment. The epoxidation reaction provides alkyl or aryl glycidic amides in good to excellent yields and exclusive trans selectivity. Finally, through of a chemospecific 6-exo-tet ring closure of trans-epoxyamides we access to morpholin-3-ones densely functionalized with excellent chemical and stereochemical yields. [Display omitted]