Amino acid , thermal generation

In an extensive study into the application of the decarboxylative approach to azomethine ylides, Giigg reported the construction of numerous, complex polycyclic systems via an intramolecular protocol. Thiazolidine-4-carboxylic acid (263) was shown to react with 264 in refluxing toluene to furnish a 2 1 mixture of 265 and 266 in 63% yield (81). The reaction is assumed to occur via condensation of the aldehyde and amino acid to generate the imine 267, followed by cyclization to 268. Subsequent thermal decarboxylation of the ester generates either a syn dipole leading to 265 from an exo transition state, or an anti dipole and endo transition state generating adduct 266 (Scheme 3.90). 

Photodriven reactions of Fischer carbenes with alcohols produces esters, the expected product from nucleophilic addition to ketenes. Hydroxycarbene complexes, generated in situ by protonation of the corresponding ate complex, produced a-hydroxyesters in modest yield (Table 15) [103]. Ketals,presumably formed by thermal decomposition of the carbenes, were major by-products. The discovery that amides were readily converted to aminocarbene complexes [104] resulted in an efficient approach to a-amino acids by photodriven reaction of these aminocarbenes with alcohols (Table 16) [105,106]. a-Alkylation of the (methyl)(dibenzylamino)carbene complex followed by photolysis produced a range of racemic alanine derivatives (Eq. 26). With chiral oxazolidine carbene complexes optically active amino acid derivatives were available (Eq. 27). Since both enantiomers of the optically active chromium aminocarbene are equally available, both the natural S and unnatural R amino acid derivatives are equally... 

Reaction selectivity of the parent ortho-QM has also been explored with a variety of amino acid and related species.30 In these examples, the rates of alkylation and adduct yields were quantified over a range of temperatures and pH values. The initial QM3 was generated by exposing a quaternary benzyl amine (QMP3) to heat or ultraviolet radiation (Scheme 9.10). Reversible generation of QM3 was implied by subsequent exchange of nucleophiles at the benzylic position under alternative photochemical or thermal activation.30 Report of this work also included the first suggestion that the reversible nature of QM alkylation could be used for controlled delivery of a potent electrophile. 

It is demonstrated that a great many flavor compounds are formed in both model systems. On the other hand, phenylalanine formed by aldol condensations some special aroma products. Furthermore, the generation of thermal aroma compounds depend on the pH, the sugar/amino acid ratio and the temperature. 

Formation of Amino Acid Specific Maillard Products and Their Contribution to Thermally Generated Aromas... 

The first two sections of this book provide the reader with a background on the thermal generation of aromas. Included in these sections are perspectives on the regulatory aspects and the analytical methodologies at the forefront of aroma research. Subsequent sections present original research on aromas derived from various food sources. In addition, we have included a section on mechanistic studies to provide insights into aroma formation through thermal decomposition of lipid, carbohydrate, and amino acid precursors. The final section is entirely... 

Conspecifics have also proven useful in discerning the difference in temperature needed to foster adaptive change and the amounts of sequence change needed to generate this adaptation. Powers et al. (1993) have shown that in the killifish Fundulus heteroclitus only one or two amino acid substitutions are sufficient to explain the differences in kinetics and thermal stability of LDH-B variants in northern and... 

The last variation of the oxazoline route is a cycloreversion of 5-oxazoli-dinones or oxazolidines. Thermal decarboxylation of 5-oxazolidinones is a convenient method of generating nonstabilized azomethine ylides, since the heterocyclic precursors are accessible, and sometimes isolable, by simply heating a-amino acids and carbonyl compounds. This has been discussed in Section II,E. 

The major precursors in meat flavors are die water-soluble components such as carbohydrates, nucleotides, thiamine, peptides, amino acids, and the lipids, and Maillard reaction and lipid oxidation are the main reactions that convert these precursors in aroma volatiles. The thermal decomposition of amino acids and peptides, and the caramelization of sugars normally require temperatures over 150C for aroma generation. Such temperatures are higher than those normally encountered in meat cooking. During cooking of meat, thermal oxidation of lipids results in the formation of many volatile compounds. The oxidative breakdown of acyl lipids involve a free radical mechanism and the formation of... 

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