polymer-supported cinchona alkaloid-derived ammonium salts as recoverable phase-transfer catalysts for the asymmetric synthesis of α-amino acids聚合物固载金鸡纳碱,提取盐铵可恢复控制相α-amino酸不对称合成的催化剂.pdf

Molecules 2004, 9, 349-364 molecules ISSN 1420-3049 Polymer-Supported Cinchona Alkaloid-Derived Ammonium Salts as Recoverable Phase-Transfer Catalysts for the Asymmetric Synthesis of α-Amino Acids† Rafael Chinchilla, Patricia Mazón and Carmen Nájera* Departamento de Química Orgánica and Instituto de Síntesis Orgánica (ISO), Universidad de Alicante, Apdo. 99, 03080 Alicante, Spain. Tel.: (+34) 965 903728, Fax: (+34) 965 903549. * Author to whom correspondence should be addressed; e-mail: cnajera@ua.es † Dedicated to Prof. Ramón Mestres on the occasion of his 65th anniversary. Received: 2 March 2004 / Accepted: 22 March 2004 / Published: 30 April 2004 Abstract: Alkaloids such as cinchonidine, quinine and N-methylephedrine have been N-alkylated using polymeric benzyl halides or co-polymerized and then N-alkylated, thus affording a series of polymer-supported chiral ammonium salts which have been employed as phase-transfer catalysts in the asymmetric benzylation of an N-(diphenylmethylene)glycine ester. These new polymeric catalysts can be easily recovered by simple filtration after the reaction and reused. The best ee’s were achieved when Merrifield resin-anchored cinchonidinium ammonium salts were employed. Keywords: Amino acids, asymmetric synthesis, phase-transfer catalysis, chiral ammonium salts. Introduction The synthesis of optically active α-amino acids using simple and easily scalable procedures is an important synthetic challenge due to their industrial interest [1]. Amongst all the repor