Collect. Czech. Chem. Commun. 2000, 65, 425-433

Spirocyclization of Isatin with Chiral α-Aminothiols: Diastereoselective Synthesis of (-)- and (+)-4'-(Methoxycarbonyl)spiro[indoline-3,2'-thiazolidin]-2-one

Peter Kutschya,*, Mojmír Suchýa, Milan Dzurillaa, Pavel Pazderab, Mitsuo Takasugic and Vladimír Kováčikd

a Department of Organic Chemistry, Faculty of Natural Sciences, P. J. Šafárik University, Moyzesova 11, 041 67 Košice, Slovak Republic
b Department of Organic Chemistry, Faculty of Natural Sciences, Masaryk University, Kotlářská 2, 61 137 Brno, Czech Republic
c Division of Material Sciences, Graduate School of Environmental Earth Science, Hokkaido University, Sapporo 060-0810, Japan
d Institute of Chemistry, Slovak Academy of Sciences, Dúbravská cesta 9, 842 38 Bratislava, Slovak Republic


Reactions of isatin with chiral α-aminothiols have been studied. With L-cysteine, only decomposition products were formed under various reaction conditions, whereas D- and L-penicillamine afforded mixtures of diastereomeric 4'-carboxy-5',5'-dimethylspiro[indoline- 3,2'-thiazolidin]-2-ones (4a and 4b or 5a and 5b) in the ratio 1 : 1. The reaction of isatin with methyl L- and D-cysteinates under mild reaction conditions (methanol-benzene, room temperature) proceeded diastereoselectively with the formation of (-)- and (+)-4'-(methoxycarbonyl)spiro[indoline-3,2'-thiazolidin]-2-one (6a and 8) in 38 and 30% yields, respectively. Optically inactive 4'-(methoxycarbonyl)spiro[indoline-3,2'-([2',5']dihydrothiazol)]-2-one (7) was isolated as a side product in 7 and 3% yield, respectively. Structure of the obtained products was determined by spectral methods, including NOE difference measurements and by X-ray crystallography.

Keywords: Phytoalexins; Indoles; Thiazolidines; Diastereoselective spirocyclization; Cysteine; Penicillamine.

References: 35 live references.