Stereochemistry and biosynthesis

Lourith, N., Katayama, T., and Suzuki, T., 2005, Stereochemistry and biosynthesis of 8-0-4 neolignans in Eucommia ulmoides diastereoselective formation of guaiacylglycerol 8-0-4 -(sinapyl alcohol) ether, J. Wood Sci. 51 370-378. 

Rahman, M. A., Katayama, T., Suzuki, T., Yoshihara, Y. and Nakagawa, T. (2007) Stereochemistry and biosynthesis of (-1-)—lyoniresinol, a syringyl tetrahydronaphthalene lignan in Lyonia ovalifolia var. elliptica It feeding experiments with C labeled precursors. /. INood Set, 53,114—20. 

Funayama et al. reported the possibility for the application of their model to the stereochemistry and biosynthesis of the Imown benzenoid ansamycin antibiotics [202]. According to the analysis, herbimycin A (86) seemed to possess the same biosynthetic building units as those of... 

Corey, E.J., De, B Ponder, J.W., and Berg, J.M. (1984) The stereochemistry and biosynthesis of hybridalactone, an eicosanoid from Laurencia hybrida. Tetrahedron Lett, 25,1015-1018. 

Silva, C.J. and Djerassi, C. (1991) Sterols in marine invertebrates. Part 64. Isolation, stereochemistry, and biosynthesis of sormosterol, a novel cyclopropane-containing sponge sterol. Collect. Czech. Chem. Commun., 56, 1093-1105. 

Some male arctiid moths produce their courtship pheromone from dietary pyrrolizidine alkaloids acquired during feeding by the larvae [ 126]. Conversion of monocrotaline to hydroxydanaidal by males is accomplished by aromatiza-tion, ester hydrolysis and oxidation of an alcohol to the aldehyde [7]. In the case of Utetheisa ornatirx the stereo-configuration at C7 of the dietary alkaloid is the same as the pheromone released (R). In contrast, another arctiid, Creatono-tos transiens, can convert a dietary precursor alkaloid with the (S) configuration at C7 (heliotrine) to (l )-hydroxydanaidal. The biosynthesis occurs by first oxidation-reduction at C7 to convert the stereochemistry and then proceeds through aromatization, hydrolysis, and oxidation [7]. 

Some of the most interesting applications of organic structural theory to the elucidation of biosynthetic pathways were stimulated by efforts to formulate mechanisms for the biosynthesis of alkaloids. Conversely, consideration of implied biogenetic relations have occasionally helped structural determination. An important aspect of theories concerning alkaloid biosynthesis has been the assumed role of the aromatic amino acids in their formation. Only limited experimental evidence is available in this area. The incorporation of tyrosine- 8-C into morphine has been shown to be in accordance with a theory for its formation from 3,4-dihydroxyphenyl-alanine plus 3,4-dihydroxyphenylacetaldehyde. A stimulating theory of the biosynthesis of indole alkaloids, based on a condensation between trypt-amine and a rearrangement product of prephenic acid, has recently been published. The unique stereochemistry of C15 of these alkaloids had an important part in the formulation of the theory. Experimental proof of this theory would be valuable for several areas of alkaloid chemistry and biosynthesis. 

Haynes RK. From artemisinin to new artemisinin antimalarials Biosynthesis, extraction, old and new derivatives, stereochemistry and medicinal chemistry requirements. Curr. Top. Med. Chem. 2006 6 509-537. 

Fig. 14.1-4)[411. This compound is an important intermediate in the shikimate pathway for the biosynthesis of aromatic amino acids in plants. The RAMA reaction produced the desired d-threo stereochemistry, and chemical reduction of the keto group gave the desired (6R)-stereoisomer in 60% diastereomeric excess. Other analogs of DAHP are also potentially available by this route, due to the broad substrate specificity of RAMA.

P. J. Keller Q. Le Van S. U. Kim D. H. Bown H. C. Chen A. KohnIe A. Bacher H. G. Floss, Biochemistry 1 8,27,1117-1120. M. Fischer L. Chatwell W. Romisch W. Eisenreich R. Huber T. Krojer A. Bacher, Biosynthesis ot Riboflavin. Stereochemistry and X-ray Structure ot 2,5-Diamino-6-Ribitylamino-4(3H)-Pyrimidinone 5 -Phosphate Synthase ot Methanococcus jannaschii. In Flavins Flavoproteins, Proceedings ot the 15th International Symposium. ARchiTect Inc., 2005 pp 725-730. 

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