Synthesis of Pyranopyrans Related to Diplopyrone and Evaluation as Antibacterials and Herbicides
Synthesis of Pyranopyrans Related to Diplopyrone and Evaluation as Antibacterials and Herbicides
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DOI：
10.1021/acs.jafc.0c02564
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发表时间：
2020-09-16
影响因子：
6.1
通讯作者：
Giuliano, Robert M.
中科院分区：
文献类型：
--
作者：
Roireau, Jack H.;Rosano, Robert J.;Giuliano, Robert M.
立体选择性合成的新的吡喃吡喃，涉及的天然产物diplopyrone，这是一种植物毒素的软木橡树衰退，已经实现了从碳水化合物的起始材料，在两种方法的基础上的C-糖苷作为关键中间体。通过Ferrier重排制备的C-炔基糖苷被用作新的吡喃吡喃炔的前体，该吡喃炔对引起鲶鱼肠败血症的常见细菌病原体爱德华氏菌（Edwardsiella ictaluri）显示出有效的抗菌活性。C-炔基糖苷也表现出除草活性。在温室研究中获得了吡喃吡喃腈（4aR，6S，8aR）-6-氰基-6，8a-二氢吡喃并-[3，2-B]吡喃-2（4aH）-酮的新的生物测定数据，该数据是迄今为止合成的最有效的吡喃吡喃类化合物，显示了额外的除草活性。合成的其他新类似物包括通过Isobe C-炔基化-重排/还原和基于RCM的吡喃吡喃结构制备的去甲基吡喃吡喃。在这项研究中合成的新的吡喃并吡喃的抗生素和植物毒性活性突出了非内酯环上的取代基的重要性，并展示了这种化合物作为抗生素和除草剂的潜力。
Stereoselective syntheses of new pyranopyrans that are related to the natural product diplopyrone, which is a phytotoxin implicated in cork oak decline, have been achieved from carbohydrate starting materials in two approaches that are based on C-glycosides as key intermediates. A C-alkynyl glycoside prepared by Ferrier rearrangement was used as the precursor to a new pyranopyran alkyne that showed potent antibacterial activity against the common bacterial pathogen Edwardsiella ictaluri that causes enteric septicemia in catfish. The C-alkynyl glycoside also showed herbicidal activity. New bioassay data for the pyranopyran nitrile (4aR,6S,8aR)-6-cyano-6,8a-dihydropyrano-[3,2-b]pyran-2(4aH)-one, the most potent of the pyranopyrans synthesized to date, were obtained in greenhouse studies that revealed additional herbicidal activity. Other new analogues that were synthesized included desmethylpyranopyrans that were prepared by Isobe C-alkynylation-rearrangement/reduction and RCM-based pyranopyran construction. The antibiotic and phytotoxic activities of the new pyranopyrans synthesized in this study highlight the importance of substituents on the nonlactone ring and demonstrate the potential of such compounds as antibiotics and herbicides.