TY - JOUR
T1 - Reactivity of chlorodeoxypseudoephedrines with oxo-, thio-, and selenocyanates
AU - Cruz, Alejandro
AU - Padilla-Martínez, Itzia Irene
AU - García-Báez, Efrén V.
AU - Contreras, Rosalinda
N1 - Funding Information:
A. Cruz thanks Secretaría de Investigación y Posgrado del IPN (SIP-IPN) for financial support, Grant 20060502.
PY - 2007/1/31
Y1 - 2007/1/31
N2 - Herein, the reactivity of chlorodeoxypseudoephedrine hydrochlorides with oxo-, thio-, and selenocyanate nucleophiles is reported. 1,3-Heterazolidine-2-iminium or ammonium salts were obtained stereoselectively in most cases. The hard-soft nature of the calcogen atom determines the mechanistic pathway via an SN2 (X = O), aziridine intermediate (X = Se), or both (X = S). A simple method to synthesize stereoselectively the trans-isomer of 3,4-dimethyl-5-phenyl-oxazolidine-2-iminium chloride and the cis-isomer of 4-methyl-5-phenyl-oxazoline-2-ammonium chloride, was also found. In addition, heterazolidine-2-imines or amines were liberated from the corresponding salts [Cl- or XCN- (X = O, S, Se)] with aqueous NaOH. Finally, cis-3,4-dimethyl-5-phenyl-oxazolidine-2-iminium chloride, cis-4-methyl-5-phenyl-oxazoline-2-amine, and trans-4-methyl-5-phenyl-selenazoline-2-amine compounds were studied by X-ray diffraction.
AB - Herein, the reactivity of chlorodeoxypseudoephedrine hydrochlorides with oxo-, thio-, and selenocyanate nucleophiles is reported. 1,3-Heterazolidine-2-iminium or ammonium salts were obtained stereoselectively in most cases. The hard-soft nature of the calcogen atom determines the mechanistic pathway via an SN2 (X = O), aziridine intermediate (X = Se), or both (X = S). A simple method to synthesize stereoselectively the trans-isomer of 3,4-dimethyl-5-phenyl-oxazolidine-2-iminium chloride and the cis-isomer of 4-methyl-5-phenyl-oxazoline-2-ammonium chloride, was also found. In addition, heterazolidine-2-imines or amines were liberated from the corresponding salts [Cl- or XCN- (X = O, S, Se)] with aqueous NaOH. Finally, cis-3,4-dimethyl-5-phenyl-oxazolidine-2-iminium chloride, cis-4-methyl-5-phenyl-oxazoline-2-amine, and trans-4-methyl-5-phenyl-selenazoline-2-amine compounds were studied by X-ray diffraction.
UR - http://www.scopus.com/inward/record.url?scp=33846847888&partnerID=8YFLogxK
U2 - 10.1016/j.tetasy.2006.12.012
DO - 10.1016/j.tetasy.2006.12.012
M3 - Artículo
SN - 0957-4166
VL - 18
SP - 123
EP - 130
JO - Tetrahedron Asymmetry
JF - Tetrahedron Asymmetry
IS - 1
ER -