High-value alcohols and higher-oxidation-state compounds by catalytic Z-selective cross-metathesis
High-value alcohols and higher-oxidation-state compounds by catalytic Z-selective cross-metathesis
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DOI：
10.1038/nature14061
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发表时间：
2015-01-08
期刊：
影响因子：
64.8
通讯作者：
Hoveyda, Amir H.
中科院分区：
文献类型：
--
作者：
Koh, Ming Joo;Khan, R. Kashif M.;Hoveyda, Amir H.
烯烃复分解催化剂为生命科学领域的医生和研究人员提供了不可缺少的分子（1,2）。然而，一个持续存在的问题是，缺乏直接生成无环Z烯丙醇的化学转化，包括含有受阻相邻取代基或活性功能单元（如苯酚、醛或羧酸）的产物。在这里，我们提出了一种电子修饰的二硫化钌催化剂，可以有效地通过交叉复分解产生高价值的化合物。钌配合物由市售前驱体和易于生成的空气稳定型儿茶硫酸锌制备。在环境条件下，通常用5.0摩尔的络合物和廉价的反应伙伴在4-8小时内进行转化；产品收率高达80%，Z:E非对映选择性为98:2。该催化剂用于合成天然抗肿瘤剂neopeltolide和可再生原料（油酸）单步立体选择克级转化为抗真菌剂。在这种转化中，新催化剂比常用的二氯钌配合物更有效地促进交叉复分解，表明其用途可能超出z选择过程。
Olefin metathesis catalysts provide access to molecules that are indispensable to physicians and researchers in the life sciences(1,2). A persisting problem, however, is the dearth of chemical transformations that directly generate acyclic Z allylic alcohols, including products that contain a hindered neighbouring substituent or reactive functional units such as a phenol, an aldehyde, or a carboxylic acid. Here we present an electronically modified ruthenium-disulfide catalyst that is effective in generating such high-value compounds by cross-metathesis. The ruthenium complex is prepared from a commercially available precursor and an easily generated air-stable zinc catechothiolate. Transformations typically proceed with 5.0 mole per cent of the complex and an inexpensive reaction partner in 4-8 hours under ambient conditions; products are obtained in up to 80 per cent yield and 98:2 Z:E diastereoselectivity. The use of this catalyst is demonstrated in the synthesis of the naturally occurring anti-tumour agent neopeltolide and in a single-step stereoselective gram-scale conversion of a renewable feedstock (oleic acid) to an anti-fungal agent. In this conversion, the new catalyst promotes cross-metathesis more efficiently than the commonly used dichloro-ruthenium complexes, indicating that its utility may extend beyond Z-selective processes.