62 カルベンとイオウの反応性を利用した数種のピロリチジンアルカロイド類およびペネム、カルバペネムの合成(口頭発表の部)

概要

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Recently we have been Involved in the development of a new carbon-carbon bond forming reaction via the rearrangement of sulfur ylide intermediates which were easily prepared by the preferential interaction of a carbene or carbenoid with divalent sulfur. This synthetic strategy was applied to the synthesis of pyrrolizidine alkaloids as follows. Intramolecular treatment of 5-phenylthiopyrrolidone derivative having organodiazo function in the presence of rhodium (II) acetate brought about the carbon-carbon bond formation at the position previously occupied by sulfur atom to give the bicyclic compounds which were then converted to (±)-isoretronecanol, (±)-trachelanthamidene, and (±)-supinidine. Whereas the intermolectlar reaction of an opticaly active 4-hydroxy-5-phenylthlopyrrolidone derivative with α-diazo-malonate yielded the carbon introduced product stereoselec-tively at the a-position to nitrogen atom, and this product was successfully transformed into (+)-heliotridine and (+)-retronecine. Moreover, the construction of carbapenem and penem ring skeleton was achieved through its 2,3-bond formation by application of the oxalimide cyclization with thioacetal group. This results supports the reaction mechanism involving a carbene species.
天然有機化合物討論会の論文
1988-09-26