Silva Franck, Sawicki Marcin, Gouverneur Véronique
Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, OX1 3TA Oxford, UK.
Org Lett. 2006 Nov 9;8(23):5417-9. doi: 10.1021/ol0624225.
[Structure: see text] For the first time, unmodified ynones were used in organocatalytic asymmetric aldol reactions delivering monoprotected anti-alpha,beta-dihydroxyynones in high yields, dr's up to 19:1, and ee's up to 95%. These products can be either reduced to afford enantioenriched unsaturated anti,anti-triol or cyclized using a novel intramolecular phosphine-catalyzed alpha-addition to the ynone. This organocatalytic sequential aldol-cyclization process provides a concise entry to unusual enantioenriched oxygenated heterocycles, which can be used for subsequent structural manipulations.
[结构：见正文] 首次将未修饰的炔酮用于有机催化不对称羟醛反应，以高收率得到单保护的反式α,β-二羟基炔酮，非对映选择性高达19:1，对映体过量率高达95%。这些产物既可以还原得到对映体富集的不饱和反式、反式-三醇，也可以使用新型分子内膦催化的α-加成到炔酮上进行环化。这种有机催化的连续羟醛-环化过程为合成不寻常的对映体富集的含氧杂环提供了一条简洁的途径，这些杂环可用于后续的结构修饰。
