Nobel synthetic methodologies

Equation (1.8) also shows how redox reactions are intricately linked to substitution. As Taube stated in his Nobel lecture While substitution reactions can be discussed without concern for oxidation reduction reactions, the reverse is not true. The substitution properties of both cobalt(III) and cobalt(II) metal ions provides the rationale for this synthetic methodology. 

Figure 14. Examples of Nobel metal-catalyzed synthetic methodologies.

This reaction, now termed hydroboration, has opened up the quantitative preparation of organoboranes and these, in turn, have proved to be of outstanding synthetic utility. It was for his development of this field that H. C. Brown (Purdue) was awarded the 1979 Nobel Prize in Chemistry . Hydroboration is regiospecific, the boron showing preferential attachment to the least substituted C atom (anti-Markovnikov). This finds ready interpretation in terms of electronic factors and relative bond polarities (p. 144) steric factors also work in the same direction. The addition is stereospecific cis (syn). Recent extensions of the methodology have encompassed the significant development of generalized chiral syntheses. 

In 1990, the Nobel Prize in Chemistry was awarded to E. J. Corey for the development of the theory and methodology of organic synthesis . As was summarized in Corey s Nobel lecture, the essence of his research was in advancing the level of synthetic science by an approach consisting of three integral components the development of more general and powerful ways of... 

The methodology of solid phase peptide synthesis (SPPS) [65, 66] has been credited with the award of 1984 Nobel Prize in chemistry [67] to its inventor, Bruce R. Merrifield of the Rockefeller University. At the heart of the SPPS lies an insoluble polymer support or gel , which renders the synthetic peptide intermediates insoluble, and hence readily separable from excess reagents and by-products. In addition to peptide synthesis, beaded polymer gels are also being studied for a number of other synthetic and catalytic reactions [2]. Ideally, the polymer support should be chemically inert and not interfere with the chemistry under investigation. The provision of chemical inertiKss presents no difficulty, but the backbone structure of the polymer may profoundly influence the course of the reaction on the polymer support. This topic has attracted considerable interest, particularly in relation to the properties of polystyrene (nonpolar, hydrophobic), polydimethylacrylamide (polar, hydrophilic), and copoIy(styrene-dimethylaciylamide) (polar-nonpolar, amphiphilic) (see later). 

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