Application of Intramolecular 1,3‐Dipolar Cyclic Addition of Azide and Olefin; Construction of (Pyrrolidine‐2‐ylidene)glycinate and Glycinamides.

Abstract

Construction of (Pyrrolidine-2-ylidene)glycinate and Glycinamides. -Pyrrolidineylidene glycine-amide (XII) and glycinate, which are important fragments of antitumor antibiotics, are synthesized from arabinal (I) utilizing the title reaction, cf. (XI)→(XII), as a key reaction. Initial Horner-Emmons reaction of (I) with reagent (II), followed by condensation of hydrolysis product (V) and amino alcohol (VI) yields, after oxidation of amide alcohol (VII), the desired ketone (VIII). The removal of the Tbs-protecting group is carried out by using pyridine as a mixed solvent to prevent Z-E isomerization by strong acid hydrogen fluoride. Alcohol (IX) is obtained as mixture of conformational isomers. The monochloromethanesulfonyl group is the appropriate leaving group for conversion of (IX) to azide. -(KONDA-YAMADA*, Y.; ASANO, K.; SATOU, T.; MONMA, S.; SAKAYANAGI, M.; SATOU, N.; TAKEDA, K.; HARIGAYA, Y.; Chem. Pharm. Bull. 53 (2005) 5, 529-536; Sch. Pharm. Sci., Kitasato Univ., Minato, Tokyo 108, Japan; Eng.) -H. Hoennerscheid 46-195