Wu Jessica, Verboom Katherine L, Krische Michael J
University of Texas at Austin, Department of Chemistry, 105 E 24th St., Welch Hall (A5300), Austin, Texas 78712, United States.
Chem Rev. 2024 Dec 25;124(24):13715-13735. doi: 10.1021/acs.chemrev.4c00858. Epub 2024 Dec 6.
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.
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转移反应进行了分类，并描述了它们在聚酮天然产物全合成中的应用。这些方法利用了一种氧化还原过程，其中醇的氧化通过从不饱和烃前亲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到醛的氧化还原反应。此外，在仲醇存在下伯醇的化学选择性脱氢能够在无保护基团的情况下实现碳-碳偶联。
