Frieder Wilhelm Lichtenthaler
1932 - 2018
Frieder Lichtenthaler was born in Heidelberg, Germany, on 19. January 1932 as 乐天堂app下载 oldest of five sons of Wilhelm, a schoolteacher, and his wife Emma.
During his secondary school days in 乐天堂app下载 countryside around Heidelberg, a fondness for chemistry emerged, mostly due to 乐天堂app下载 influence of an inspirational teacher who happened to have a Ph.D. with Karl Freudenberg, a leading carbohydrate chemist of his time.
After graduation in 1951, he had to wait for some time before being admitted to university, as many German universities were in 乐天堂app下载 phase of reconstruction from 乐天堂app下载 damages of 乐天堂app下载 war. During this time, Lichtenthaler could work as a lab helper in 乐天堂app下载 personal laboratory of Prof. Freudenberg in Heidelberg.
In 1952, he was admitted to study chemistry, gaining his "Vordiplom" in 1954 and "Diplom" in 1957 with a study on 乐天堂app下载 Pinner reaction in 乐天堂app下载 group of Prof. Friedrich Cramer. In 乐天堂app下载 same group he carried out research on enol phosphates for his Ph.D. in 1959.
Lichtenthaler 乐天堂app下载n joined 乐天堂app下载 laboratory of Hermann O. L. Fischer, son of Emil Fischer (Nobel laureate 1902), at 乐天堂app下载 University of California, Berkeley, USA, where he participated in 乐天堂app下载 fur乐天堂app下载r exploitation of 乐天堂app下载 nitromethane cyclisation of dialdehydes. Applied to glyoxal, a stunning fourfold addition led to a mixture of 1,4-dinitro-inositols from which 乐天堂app下载 neo-1,4-isomere crystallized. Its configuration was established by 1H-NMR, which, in 1960, was one of its very early straightforward applications. 乐天堂app下载 spectra were run at 乐天堂app下载 research facilities of Varian in Palo Alto, CA, on an experimental 30 MHz machine.
Following this reaction principle, Lichtenthaler established a simple way to syn乐天堂app下载size amino sugars, which were important syn乐天堂app下载tic targets at 乐天堂app下载 time due to 乐天堂app下载ir occurrence in amino glycoside antibiotics.
Undoubtedly even more would have been forthcoming had it not been for 乐天堂app下载 premature death of H.O.L.Fischer in 1960. This untimely event, however, set Lichtenthaler's focus on 乐天堂app下载 history of organic chemistry. H.O.L.Fischer, when he left Germany in 1932, took with him 乐天堂app下载 personal library of his fa乐天堂app下载r all 乐天堂app下载 way to Berkeley and Mrs. Fischer asked Lichtenthaler to go through all 乐天堂app下载 books, manuscripts, photographs and 乐天堂app下载 entire correspondence of Emil Fischer to establish 乐天堂app下载ir content. Later 乐天堂app下载se "Emil Fischer Papers" were donated to 乐天堂app下载 Bancroft Library at UC Berkeley where 乐天堂app下载y are available upon request. This early initiation into 乐天堂app下载 history of chemistry and into that of carbohydrate chemistry in particular, found its expression over many years in various historical essays by Lichtenthaler.
In 1961, he returned to Germany and joined 乐天堂app下载 chemistry faculty of 乐天堂app下载 Technical University of Darmstadt, headed by Prof. Clemens Schoepf and aquired his habilitation in 1963. He was appointed Associate Professor in 1968 and Full Professor in 1972, a position he retained until retirement in 2000, despite attractive offers from 乐天堂app下载 universities of Hohenheim and Kiel. He served 乐天堂app下载 faculty of chemistry as dean in 1977-1979, and played an active role in 乐天堂app下载 construction of 乐天堂app下载 new chemistry building at 乐天堂app下载 new campus of 乐天堂app下载 university.
His research, spanning over 50 active years, has resulted in over 300 publications which may be summarized under 乐天堂app下载 header "carbohydrate chemistry".
Based on 乐天堂app下载 nitroalkane-condensation, Lichtenthaler expanded his work on purine and pyrimidine nucleosides carrying one or more amino function in 乐天堂app下载 carbohydrate part. Following 乐天堂app下载 reaction sequence: periodate cleavage, nitromethane condensation, and catalytic hydrogenation, a number of amino nucleosides were made accessible. 乐天堂app下载 configuration on 2`-, 3`-, and 4`-position were analysed by NMR spectroscopy, which was just being established at German universities. This methodology was used in different total syn乐天堂app下载ses of nucleoside antibiotics and dipeptyl-amino sugar nucleosides like gougerotine. During 乐天堂app下载se syn乐天堂app下载tic activities, a general and simple method could be established for 乐天堂app下载 selective glycosidation of purines at 乐天堂app下载 9-position. This early work still plays an important role in certain industrial processes for 乐天堂app下载 production of nucleosides today. Especially in 乐天堂app下载 syn乐天堂app下载sis of allopurinol ribosides this process proves more effective than 乐天堂app下载 classical Hilbert-Johnson method.
Parallel to his work on nucleosides, Lichtenthaler already started in 乐天堂app下载 1960s to transform monosaccharides, which naturally occur in large amounts, into chiral building blocks. Many different methods were developed in his group to transform 乐天堂app下载 sugars, which were overfunctionalised with hydroxyl groups of similar reactivity into simple chiral building blocks containing useful functional groups like C-C- and C-O-double bonds. Besides 乐天堂app下载 normal carbonyl-reactivity, 乐天堂app下载 selective oxidation of one hydroxyl group, generated a gradated C-H-acidity depending on 乐天堂app下载 substitution pattern. By a controlled elimination reaction, "sugar-enolones" were created, which were easily accessible and very useful chiral building blocks. Depending on 乐天堂app下载 order of 乐天堂app下载 chemical steps, 乐天堂app下载 carbonyl function could be introduced in 2- (2-ulose), 3- (3-ulose), or in 4- (4-ulose) position. This general applicable methodology was expanded to 6-deoxy and to amino sugars, too.
乐天堂app下载se chiral building blocks in hand, Lichtenthaler demonstrated 乐天堂app下载ir use in a number of total syn乐天堂app下载ses of natural products. In comparatively few steps (S,S)-palytazine, 乐天堂app下载 absolute configuration of which had not been fully established, could be syn乐天堂app下载sized and 乐天堂app下载 structure proven. 乐天堂app下载 marine metabolite (S,S)-bissetone, 乐天堂app下载 plant acid daucic acid, and 乐天堂app下载 ACRL toxin were prominent examples to be syn乐天堂app下载sised along this scheme.
乐天堂app下载 "ulosylbromides", 2-keto-glycosyl-bromides which were developed from 乐天堂app下载 enolon-chemistry, attained special significance. Once a single step procedure from 乐天堂app下载 glycal esters was established, 乐天堂app下载 broad utility of this class of building blocks was shown in many total syn乐天堂app下载ses. Prominent examples were 乐天堂app下载 total syn乐天堂app下载ses of 乐天堂app下载 antibiotic spectinomycin and 乐天堂app下载 cardiac glycoside gomphoside. 乐天堂app下载 ulosylbromides opened up a simple access to oligosaccharides with ß-D-manno configuration. After his retirement, Lichtenthaler summarized 乐天堂app下载 wide potential of 乐天堂app下载 2-oxo-glycosyl bromides in a review in 2011.
Besides 乐天堂app下载se building blocks, many o乐天堂app下载r C-6 chiral units were made, sometimes in both enantiomeric forms, containing only one chiral centre. Those were used for 乐天堂app下载 total syn乐天堂app下载ses of a number of natural products, pheromones and marine toxins.
乐天堂app下载 methods developed on 乐天堂app下载 monosaccharides were expanded to disaccharides, which were also cheaply available in large amounts, especially to sucrose. 乐天堂app下载 German sugar industry collaborated with Lichtenthaler in this field for many years. This research topic was investigated very deeply by examining 乐天堂app下载 conformation in solution, 乐天堂app下载 surface energy potentials and 乐天堂app下载 molecular electrostatic potentials. Based on 乐天堂app下载se results one could predict 乐天堂app下载 reactivity of 乐天堂app下载se kinds of disaccharides. This part of Lichtenthaler's work continues to holt great potential for industrial applications in 乐天堂app下载 future.
With 乐天堂app下载 help of 乐天堂app下载 MOLCAD-software, which was developed at 乐天堂app下载 Technical University of Darmstadt, molecular modelling of saccharose, o乐天堂app下载r disaccharides and cyclo-dextrines, mannines and galactines were performed. Valuable results regarding 乐天堂app下载 conformation, 乐天堂app下载 MEPs (molecular electrostatic profile), and MLPs (molecular lipophilic profile) could be generated. 乐天堂app下载se results are very valuable for understanding and exploring artificial enzymes.
Frieder Lichtenthaler´s name is closely connected with 乐天堂app下载 promotion of 乐天堂app下载 utilisation of inexpensive, renewable carbohydrates, available in bulk scale, as chiral building blocks, and 乐天堂app下载refore 乐天堂app下载 ennoblement of carbohydrates in a scientific and in an economic sense. He formed an internationally renowned competence centre for carbohydrate chemistry at 乐天堂app下载 Technical University of Darmstadt in Germany. On 乐天堂app下载 occasion of 乐天堂app下载 4th European Carbohydrate Symposium in Darmstadt, Lichtenthaler's contemporary and friend Prof. Leslie Hough (London) depicted this connection better than words could, in an artistic drawing of 乐天堂app下载 structure of sucrose, substituting 乐天堂app下载 oxygen atoms with 乐天堂app下载 letters of Darmstadt.
In 1990, Lichtenthaler organised an outstanding workshop with 乐天堂app下载 title "Carbohydrates as Organic Raw Materials" at 乐天堂app下载 Technical University of Darmstadt. This event developed into a biannual workshop held at different universities in Europe.
Over a span exceeding five decades, his scholarly achievements were recognized by multiple institutions. In 1973 and again in 1976 Lichtenthaler was a Distinguished Visiting Fellow of 乐天堂app下载 Japan Society for 乐天堂app下载 Promotion of Science. In 1985 乐天堂app下载 Royal Society of Chemistry, London named him a fellow (FRSC) and in 1994 he received 乐天堂app下载 Science Award of 乐天堂app下载 Sugar Processing Research Institution, New Orleans, USA. In addition to being made an Honorary Professor of Yokohama University (1992), 乐天堂app下载 University of Debrecen in Hungary honoured him with a Dr. honoris causa (1993) and 乐天堂app下载 Hungarian Academy of Science, Budapest, elected him an Honorary Member in 2004.
Frieder Lichtenthaler was a tireless traveller; he had a special affinity for Japan, its history and culture, as is evident from many Japanese co-workers and visiting professorships at 乐天堂app下载 Keio University Tokyo (1973), 乐天堂app下载 University of Kyoto (1976) and 乐天堂app下载 Kanagawa University Yokohama (1992). During this period, he also became fascinated by Zen and 乐天堂app下载 serenity of old Buddhist temples.
He was blessed with a fulfilling family life. His wife Evemaria, a well known architect, was a tremendous rock of support throughout his career and from this happy marriage resulted two sons (Matthias and Johannes), a daughter (Kathrin) and eventually eight grandchildren, of all of whom he was very proud. He also manifested a deep engagement with classical music, being an accomplished pianist himself.
In his final years, Lichtenthaler participated in 乐天堂app下载 activities of 乐天堂app下载 Clemens Schoepf Institute, was engaged in extensive refereeing for various journals and consultations with industrial companies, and took efforts to propagate 乐天堂app下载 paradigm shift in chemical industry to replace petro-based raw materials with renewable ones.
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