Synthesis of spirothiohydantoin analogues of hydantocidin

The mode of action and the structure of a herbicide in complex with its target: binding of activated hydantocidin to the feedback regulation site of adenylosuccinate synthetase.

“…Its intriguing structure and remarkable biological properties have stimulated a considerable amount of synthetic work on the parent compound (9)(10)(11)(12)(13)(14) and its analogues (15)(16)(17)(18)(19)(20)(21)(22)(23)(24)(25). The novel injury symptoms it elicits in plants has prompted a detailed investigation of its mode of action.…”

Synthesis of Carbocyclic Hydantocidins via Regioselective and Diastereoselective Phosphine-Catalyzed [3 + 2]-Cycloadditions to 5-Methylenehydantoins

“…18,29 Other analogues of hydantocidin have involved modification of the hydantoin ring 30 and it has been shown that thiohydantocidins, where the C2 carbonyl is replaced with a thiocarbonyl, can be produced 14,31 and used without the loss of herbicidal activity. 31 We report here a new strategy for the synthesis of carbocyclic hydantocidin (3) and its 3',4'diepimer using a phosphine-catalysed [3+2]-cycloaddition of ethyl 2-butynoate 6a (6, X = OEt) with N,N'-diprotected-5-methylenehydantoins (4) to generate the key spiro-heterocyclic system of these target molecules (Scheme 1). The phosphine-catalysed [3+2]-cycloaddition of ethyl buta-2,3-dienoate or ethyl butynoate with electron-deficient alkenes has been established as a useful method for preparing substituted cyclopentenes [32][33][34][35][36][37][38][39][40][41][42][43][44][45] both in racemic and enantio-enriched forms.…”

Glycosaminosäuren und ihre Verwendung als Bausteine in der kombinatorischen Synthese sowie ihre Bedeutung für die Wirkstoff-Forschung

“…B. ist das natürlich vorkommende Spiroribofuranosehydantoin 10 ein starkes, für Mikroorganismen und tierische Lebewesen nicht toxisches Herbizid 10. Stereosiomeren und Desoxyderivaten von 10 (mit Ausnahme des 5‐Epimers) fehlt die biologische Wirkung,10, 69–76 während in Spirothiohydantoinanaloga von 10 die herbizide Wirkung erhalten blieb 77. Für die Wirkungsweise des Herbizids ist inzwischen ein Mechanismus vorgeschlagen worden 173.…”