Catalytic asymmetric synthesis of a potent thiomarinol antibiotic
Catalytic asymmetric synthesis of a potent thiomarinol antibiotic
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DOI：
10.1021/ja042827p
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发表时间：
2005-02-16
影响因子：
15
通讯作者：
Hall, DG
中科院分区：
文献类型：
--
作者：
Gao, X;Hall, DG
从ravasp互变单胞菌中分离的硫氨酸醇。11月沉没73390，是有效的海洋抗生素，具有革兰氏阳性和革兰氏阴性活性。首次实现了硫代氨基酚类海洋抗生素的全合成，全球产率达到了22%（由3-硼丙烯醛pinacolate合成）。该合成的亮点是高效的催化对映体-，区域-，E/Z-和非对映选择性三组分逆电子需求Diels - Alder/烯丙基硼化序列。这一关键操作提供了一个罕见的涉及无环2-取代烯醇醚的对映选择性HDA反应的例子，它具有不寻常但偶然的动力学选择，有利于必需的-亲二烯试剂。
Thiomarinols, isolated from the bacteriumAlteromonas ravasp. nov. SANK 73390, are potent marine antibiotics that possess both Gram-positive and Gram-negative activity. The first total synthesis of a member of the thiomarinol class of marine antibiotics was achieved in a remarkable global yield of 22% (from 3-boronoacrolein pinacolate). The highlight of this synthesis is the efficient catalytic enantio-, regio-,E/Z-, and diastereoselective three-component inverse electron demand Diels−Alder/allylboration sequence. This key operation provides a rare example of an enantioselective HDA reaction involving acyclic 2-substituted enol ethers, and it featured an unusual but fortuitous kinetic selection that favored the requisiteZ-dienophile.