Catalytic enantioselective hydrogen autotransfer reactions for the direct conversion of lower alcohols to higher alcohols are catalogued and their application to the total synthesis of polyketide natural products is described. These methods exploit a redox process in which alcohol oxidation is balanced by reductive generation of organometallic nucleophiles from unsaturated hydrocarbon pronucleophiles. Unlike classical carbonyl additions, premetalated reagents, chiral auxiliaries and discrete alcohol-to-aldehyde redox reactions are not required. Additionally, chemoselective dehydrogenation of primary alcohols in the presence of secondary alcohols enables C–C coupling in the absence of protecting groups.

中文翻译：

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醇的催化对映选择性 C-C 偶联用于超越手性助剂和预金属化试剂的聚酮总合成


对用于将低级醇直接转化为高级醇的催化对映选择性氢自动转移反应进行了分类，并描述了它们在聚酮天然产物总合成中的应用。这些方法利用氧化还原过程，其中醇氧化通过从不饱和烃原核试剂还原生成有机金属亲核试剂来平衡。与经典的羰基加成不同，不需要预金属化试剂、手性助剂和离散的醇-醛氧化还原反应。此外，在仲醇存在下伯醇的化学选择性脱氢能够在没有保护基团的情况下实现 C-C 偶联。