Sulfoxides chemistry

Methionine sulfoxide chemistry and biochemistry TABLE 6. Requirements for the reduction of Met(0)-a-l-PI ... 

Undoubtedly, one of the major interests in platinum-metal sulfoxide chemistry is the synthesis and use of O-bonded sulfoxide complexes as reactive intermediates in synthetic and catalytic chemistry. The chemistry of such weakly bonded intermediates has recently been reviewed (142). 

In the penam series, the starting materials for the functionalization of one of the C-2 methyl groups are the chloro-70a, bromo- 70b, or oxycarbonyl 70c derivatives, obtained from the usual penam sulfoxide chemistry (Figure 10)... 

Aamouche A, Devlin FJ, Stephens PJ, Drabowicz J, Bujnicki B, Mikolajczyk M. Vibrational circular dichroism and absolute configuration of chiral sulfoxides tert-butyl methyl sulfoxide. Chemistry A European Journal 2000 6 4479 1486. 

Unlike the carbonyl, the unconjugated sulfoxide is not associated with a long wavelength absorption of its own. Therefore most of what is reported herein has to do with conjugated sulfoxides. Aliphatic sulfoxides are treated separately, though there are many commonalities with aromatic sulfoxide chemistry. The aliphatic compounds have been examined by gas phase physical chemistry mediods, which also justify a separate treatment. 

An important area of sulfoxide chemistry not covered elsewhere in this review involves the synthetic utility that arises as a result of the capacity of sulfur to stabilize a negative charge on an adjacent carbon atom. This property has been studied extensively in the area of carbon-carbon bond formation [63]. 

As previously described, one of the major advances in penicillin sulfoxide chemistry in the last few years has been the rearrangement of the sulfoxide to the exomethylenecephem. The importance of this reaction resides in its utility in the successful synthesis of the clinically important oral antibiotic, cefaclor (388) (Volume 1, Chapter 2). The exomethylene isomer has also been utilized as an intermediate for the synthesis of the naturally occurring acetoxymethyl-substituted cephems. 

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