Conformationally constrained serine analogues: synthesis of new 2-amino-3-hydroxynorbornanecarboxylic acid derivatives.
A synthesis of the new oxazolone 2, functionalized with the ethoxycarbonyloxy group on methylenic carbon, is presented, starting from 4-hydroxymethylenoxazolone 1 and ethyl chlorocarbonate. Oxazolone 2 was reacted with cyclopentadiene in the presence of EtAlCl(2), giving the two diastereoisomeric cycloadducts exo-3 and endo-3 in a 70:30 ratio. Selective hydrolysis of the lactone ring (THF, HCl) gave the corresponding acids 5 and 6 which were transformed into hydroxyacid derivatives 7 and 8, respectively, operating in an ethanolic solution of Me(2)NH. The new 3-hydroxy-2-aminonorbornane-2-carboxylic acids 11 and 12, in which the serine skeleton is included, were obtained by reduction of acids 5 and 6 to derivatives 9 and 10 and a subsequent hydrolysis with HCl.
Clerici
F
F
Istituto di Chimica Organica, Facoltà di Farmacia, Centro Interuniversitario di Ricerca sulle Reazioni Pericicliche e Sintesi di Sistemi Etero-e Carbociclici, Università di Milano, Via Venezian 21, I-20133 Milano, Italy.
Gelmi
M L
ML
Gambini
A
A
D003500:Cyclization; D006868:Hydrolysis; D009682:Magnetic Resonance Spectroscopy; D009636:Norbornanes / Q000138:chemical synthesis* / Q000737:chemistry; D012694:Serine / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D013237:Stereoisomerism
D009636:Norbornanes; D012694:Serine