Isolation, Structural Determination and Synthesis of Biologically Active Substances Produced by Fungi

1.毒蘑菇Dokusasako--神经兴奋性氨基酸及其化学发展从香菇中分离得到Clipdine、Clithioneine、丙烯酸类A和B，以及4-氨基喹啉酸，但该菌中还含有其他新的有毒成分。我们试图分离它们，并发现了一种新的氨基酸和一种作为神经兴奋剂的新组份。新氨基酸的结构由波谱数据和生物发生推测出来，并经合成得到确证。以4-甲酰基吡咯-2-羧酸酯为原料合成了4-(2-羧基吡咯基)-3-丙氨酸，其结构与新的天然氨基酸相同。用手性板对合成的化合物进行了光学拆分，并测定了它们的CD。手性平板上的Rf值和天然产物的CD标记与合成的L酸相吻合。还发现了一种新的神经兴奋组分，目前正在进行结构研究。由于丙烯酸类化合物被认为是…的工具更多的神经药理学研究，因此收到了许多提供试剂的请求。研究了活性与丙烯酸类一样易得的试剂的设计和合成方法的开发。通过光诱导的Diels-Alder反应，成功地构建了具有C4取代基的吡咯烷环的高立体选择性，得到了一种新的甲氧基苯基海人藻氨酸，其神经刺激性强于丙烯酸本身。此外，对甲苯磺酸基团在Pro的C4位上的立体选择性取代反应顺利进行，建立了各种海藻氨酸的简便通用程序。2.Ohwaraitake(一种有毒蘑菇)--一种神经刺激剂和木兰素的立体化学。一种先前分离的苦味主药裸子草素A10和/或ALL可能是新的神经兴奋剂。我们在这种毒菌中寻找神经兴奋成分，测试了大鼠脊髓的去极化活性，并得出了上述结论。这种链状异戊二烯醇表现出神经兴奋活性是非常罕见和有趣的。对立体化学中的6或7个季碳或裸子林进行了合成研究。3.Hanaiguchi(一种可食用的蘑菇)--一种脂质过氧化抑制剂。从香菇中分离得到目标化合物，经波谱分析确定其结构为1-乙酰氧基-2-香叶基-4，6-二苯酚。较少

1. Dokusasako (a poisonous mushroom)-neuroexcitatory amino acids and their chemical development. Clitidine, clithioneine, acromelic acids A and B, and 4-amino quinolinic acid were isolated from the mushroom but other new poisonous principles must be contained in this fungus. We have tried to isolate them and a new amino acid and a new fraction acting as a neuroexcitant have been found. The structure of the new amino acid was deduced from spectroscopic data and its biogenesis and confirmed by the synthesis. 4-(2-Carboxypyrrolyl)-3-alanine was synthesized from 4-formylpyrrol-2- carboxylic acid ester and found to be identical with the new natural amino acid. The synthetic compound was optically resolved with a chiral plate and their CD were measured. Rf value on the chiral plate and CD sign of the natural product was coincided with synthetic L-acid. A new neuroexcitatory fraction was also found and undergoing its structural studies now. As the acromelic acids were recognized as a tool of … More neuropharmacological studies, so many requests for supplying the reagents were received. Design of the reagent which is so active as the acromelic acids and more easily accessible and development of the synthetic method of such reagents have been studied. The highly stereoselective construction of pyrrolidine ring with C4 substituent by a photo-induced Diels-Alder reaction was successfully carried out to give a new methoxyphenyl kainoid which was stronger neuroexcitant than acromelic acid itself. Furthermore, stereoselective substitution reaction of tosylate group on the C4 position of proline was smoothly performed and the easier general procedure for various kainoid was established. 2. Ohwaraitake (a poisonous mushroom)-a neuroexcitant and stereochemistry of gymnopilin. A previously isolated bitter principle gymnopilin A10 and/or All is probably new neuroexcitants. We sought for neuroexcitatory constituents in this toadstool testing depolarizing activity of a rat spinal cord and reached to the above conclusion. It is very rare and interesting that such a chain origoisoprenoid alcohol shows neuroexcitatory activity. Stereochemistry 6 or 7 quarternary carbon or the gymnopilin was under investigation by synthesis. 3. Hanaiguchi (an eddible mushroom)-a lipid peroxidation inhibitor. The title compound was isolated from the mushroom and its structure was determined as 1-acetoxy-2-geranylgeranyl-4, 6-dihydroxybenzene by spectral studies. Less