New Reactions, Improved Catalysts

Hydrogen peroxide is a more reactive but more expensive substitute for oxygen. It has a broad and relatively well-investigated metal coordination chemistry [62 a]. While it normally does not meet the tight economic requirements for the oxidative production of industrial bulk chemicals, the priority list 

Water is another ideal, environmentally sound reagent with exciting prospects, but numerous questions are still open. Could water be added to olefins in the anti-Markownikov mode Primary alcohols would thus be cheaply available (eq. (12)). Similarly, what is the appropriate catalyst to add ammonia across a double bond (hydroamination, eq. (13), Section 2.7) to yield organic amines as starting materials for a number of fine chemicals  

A new generation of polymers, e. g., Shell s Carilon, was developed from the discovery of the perfect CO/olefin alternating principle within the short time span of less than ten years. Systematic mechanistic work in this area has yielded a highly efficient carbonylation of propene (TON = 4 X 10 ) in the presence of palladium(II) catalysts to methyl methacrylate (cf. Section 1.3.2.3) [66 e]. 

It is noteworthy that the attractive homologation reaction - a formal methylene (CH2) insertion (cf. Section 3.2.7) - according to eq. (16) has received little attention as yet [67]. This synthetic principle looks promising for homologous compounds of which only one certain derivative is easily available. 

Novel C-C coupling reactions are about to enter the scope of metal complex catalysis. Examples are asymmetric aldolizations (Mukaiyama [79]), Diels-Alder reactions [80], and indium- or zinc-mediated alkylations [86]. 

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