Development of Carbohydrate Chemistry

By the middle of the nineteenth century, a number of relatively pure carbohydrates such as sucrose, cellulose from cotton, starch, glucose, fructose, mannose, and lactose were known to the chemists of Europe, especially in Germany, who were studying natural products [3]. These chemists were investigating the physical and chemical properties of carbohydrates. The following is a summary of what was known about carbohydrates in the nineteenth century. 

In the period from 1860 to 1880, the following chemical facts were known about (H-)-glucose and (+)-mannose  

They reduced Tollen s reagent, Ag(NH3)2 to Ag , indicating that they were aldehydes. 

They formed pentaacetates, indicating that they had five hydroxyl groups. 

They could be oxidized with BrfRfd to a monocarboxylic acid. 

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Because sugars are involved in most of the mechanisms established for the synthesis of these heterocycles, the development of carbohydrate chemistry has been most helpful in these researches—especially for the preparation of specifically labeled molecules. Conversely, the contribution of these efforts to carbohydrate chemistry and biochemistry has shown the involvement in biosynthesis of 1 -deoxy-D-f/rreo-pentulose—scarcely before recognized and considered a rare sugar—and of fully functionalized pentuloses of still unknown configuration (or their phosphates). Finally, evidence has been found in prokaryotes for a most extraordinary transformation of 5-amino-l-(P-D-ribofuranosyl)imidazole 5 -phos-phate into a pyrimidine. Surely, this transformation should be explained in terms... 

This issue pays tribute to two scientists who pioneered the development of carbohydrate chemistry in their respective countries of Japan and Argentina. Ibhru Komano (Kyoto) and Naoki Kashimura (Mie) describe the life and work of Konoshin Onodera, and an obituary article on Venancio Deulofeu is contributed by Rosa M. de Lederkremer and Eduardo G. Gros (Buenos Aires). 

In recent years, it has become fashionable to determine the composition of honey, and in the current literature are many reports dealing with the compositional aspects of honey from various parts of the world.65-73 It is, however, regrettable that application of paper chromatography, which has played an outstanding role in the development of carbohydrate chemistry, has not yet been fully explored in... 

In 1960 Kochetkov was elected Correspondent Member of the Academy of Sciences. In 1965 he became the coordinator of an international program on the development of carbohydrate chemistry in countries of Eastern Europe, which continued for the next twenty two years. While in the IKhPS, he became a member of the editorial boards of Carbohydrate Research, Advances in Heterocyclic Chemistry, and a number of national journals. In 1961, in collaboration with Professors Igor Torgov and Maria Botvinik, specialists in steroid and protein chemistry, Kochetkov wrote Chemistry of Natural Compounds, one of the first textbooks in this field in the country. 

The synthesis of oligosaccharides has played an important part in the development of carbohydrate chemistry. In the early days, the laboratory workers were interested mainly in preparing those compounds which normally resulted from living processes. They proved that a so-called vital force was not necessary for the production of these... 

The modest, sensitive, and unassuming approach of John Mills tended to blind one at first to the realization that here was a keen and inventive mind and an original thinker, but in subsequent discussion, his true stature became self-evident. His interest in stereochemistry was reflected in his attempt to model his life with the same care and precision that he used in building his molecules and his models. His talents were devoted mainly to the development of carbohydrate chemistry. 

Dr. Mills felt that he was tilling fertile ground, and he searched the carbohydrate literature for further examples. The result of this work was his article on The Stereochemistry of Cyclic Derivatives of Carbohydrates [This Series, 10,1-53 (1955)]. He had found his field. In the Introduction thereto he described his views on carbohydrate chemistry thus The writer, whose interests have lain mainly in the alicyclic field, has been greatly impressed by the scope that carbohydrate chemistry offers for elaborating and testing stereochemical hypotheses. Carbohydrates possess the desirable features of optical activity, crystallinity, and availability, and display a diversity in structural types and reactions that cannot be matched in other fields. . . Important contributions have, of course, already come from this source, but usually as by-products of the development of carbohydrate chemistry, rather than through the deliberate choice of carbohydrate compounds as models for experimental study. ... 

The use of sodium amalgam originates with E. Fischer. The method was a cornerstone of his aldose homologation (cyanohydrin formation, hydrolysis, lactone formation and reduction) which was so important to the development of carbohydrate chemistry. Although the yields obtained by Fischer were moderate ca. 20-50%), more recent work by Sperber et al. has resulted in significant improvements. In particular, they discovered that control of the pH of the reaction mixture was very important. At pH 3-3.5, yields in the range 52-82% were obtained with a variety of aldonolactones. As an example, the preparation of arabinose is shown in equation (4). If the pH was allowed to rise, yields were lower due to overreduction. Methyl esters of aldonic acids could also be used as substrates. 

The study of the hydrazine derivatives of sugars has played an important role in the development of carbohydrate chemistry since its inception. Phenylhydrazinc, first described in Emil Fischer s doctoral thesis, was al-... 

Today, these new possibilities assume an important significance because of the growing development of carbohydrate chemistry as a consequence of the change from petroleum as raw material to natural feedstocks. Growth of microwave-assisted chemistry in industry is also likely, because of the demonstrable possibility of moving from small-scale (g) to the multigram (kg) synthesis of carbohydrate derivatives known to be valuable intermediates in the synthesis of diverse natural products and their analogs. 

The first four chapters deal with different aspects of carbohydrate chemistry. In Chapter 1, Derek Horton discusses the development of carbohydrate chemistry and biology from antiquity to the present and beyond and summarizes the structures and methods for structural analysis of complex carbohydrates. In Chapter 2, Bo Xie and Catherine Costello review the state-of-art application of mass spectrometry to the structural analysis of complex carbohydrates. In Chapter 3, Zhongwu Guo briefly summarizes the types of glycosylation methods and synthetic strategies that are commonly used in the chemical synthesis of glycoconjugates. Enzymes have simplified the synthesis of some oligosaccharides, and in Chapter 4,... 

Table 2 The history of carbohydrate polymers and the development of carbohydrate chemistry ...

One of the great pioneers in the development of carbohydrate chemistry was Emil Fischer, who was born near Bonn, Germany, in 1852. Although he went to the University of Strasbourg to study chemistry under Friedrich Kekule, he actually obtained his Ph.D. under Adolf von Baeyer in 1874. He moved with von Baeyer to Munich, where he received his Habilitation in 1878. He was then appointed as an Ausserordentlicher, or... 

Chronological Summary of the Uses of Carbohydrates by Humans and the Development of Carbohydrate Chemistry... 

The use of halogens to oxidize carbohydrates was an early reaction used in the development of carbohydrate chemistry in the nineteenth century. The aldehyde carbon is oxidized to give an aldonic acid. 

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