Regio- and Stereoselective Homologation of 1,2-Bis(Boronic Esters): Stereocontrolled Synthesis of 1,3-Diols and Sch 725674.
Regio- and Stereoselective Homologation of 1,2-Bis(Boronic Esters): Stereocontrolled Synthesis of 1,3-Diols and Sch 725674.
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DOI：
10.1002/anie.201608406
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发表时间：
2016-11-14
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影响因子：
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通讯作者：
Aggarwal VK
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文献类型：
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作者：
Fawcett A;Nitsch D;Ali M;Bateman JM;Myers EL;Aggarwal VK
1，2-双(硼酸酯)是由端烯对映选择性二硼反应得到的，它可以在伯硼酸酯上选择性地同系化，方法是用富对映体的伯仲酸锂或苯甲酸酯生成1，3-双(硼酸酯)，然后在完全立体控制下氧化成相应的仲仲醇和仲叔醇。将该转化应用于14元大内酯SCH 725674的简明全合成。九步合成路线还包括一种新的去对称化对映体选择性二乙烯基甲醇衍生物的二硼，以及高产率的后期交叉易位反应和山口大内酯反应。
1,2‐Bis(boronic esters), derived from the enantioselective diboration of terminal alkenes, can be selectively homologated at the primary boronic ester by using enantioenriched primary/secondary lithiated carbamates or benzoates to give 1,3‐bis(boronic esters), which can be subsequently oxidized to the corresponding secondary‐secondary and secondary‐tertiary 1,3‐diols with full stereocontrol. The transformation was applied to a concise total synthesis of the 14‐membered macrolactone, Sch 725674. The nine‐step synthetic route also features a novel desymmetrizing enantioselective diboration of a divinyl carbinol derivative and high‐yielding late‐stage cross‐metathesis and Yamaguchi macrolactonization reactions.