Synthesis of (Methy1thio)penam Derivatives via Keten Addition onto 4,5-Dihydro-5-(methyIthio)-l,3-thiazolesThe 4,5-dihydro-5-(methyIthio)-2-phenyl-1,3-thiazoles 3a and 3b, easily prepared from the corresponding 1,3-thiazol-5(4H)-thiones and MeLi, react with dichloroacetyl chloride (5a) and acidoacetyl chloride (5b) in the presence of Et,N to give (methy1thio)penam derivatives 6 ( Table 1). The reaction mechanism is either a [2 + 21 cycloaddition of in situ generated ketene or a two-step reaction (Scheme 2). The structure of 6f has been confirmed by X-ray crystallography (Fig.2). The relative configuration of 6a+2 follow from comparison of their 'H-NMR spectra with those of 6f (Fig. I). The 6-addopenams 6d and 6f have been reduced to aminopenams 8a and 8b, respectively. Acylation of 8a with phenacetyl chloride yields 9 (Scheme 4 ) .