A new optically active diterpene lactone, sinulariolone [1], has been isolated as the major secondary metabolite in a Philippine collection of Sinularia flexihilis. The compound has a tricyclic structure and is more highly oxygenated than previously reported diterpenes from this species. The structure of 1 was elucidated by spectroscopy and its relative stereochemistry confirmed by single-crystal X-ray crystallography.
The mechanism of phosphine- and phosphite-induced migration of the imido group from sulfur to a
Cp ring in a tosylimido-bridged cobaltadithiolene complex was investigated, and a probable intermediate was
isolated and characterized. The presence of a large excess
of PPh3 causes the formation of the imido- and phosphine-substituted Cp complex.
The reactions of a malonate (C(COOMe)2)-bridged complex with Lewis bases give novel
sulfur ylide (M−S sulfur ylide) complex due to the cleavage of Co−C bond as determined by
X-ray sturucture analysis. Acetate (CHCOOEt)- and methylene-bridged complexes, on the
other hand, reacted with Lewis bases via an SN2 type reaction to give unstable M−S sulfur
ylide complexes and stable six-membered-ring complexes.
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