Asymmetric Protonation of Cumulenolates: Synthesis of Allenyl Aldehydes Facilitated by an Organomanganese Auxiliary.
Asymmetric Protonation of Cumulenolates: Synthesis of Allenyl Aldehydes Facilitated by an Organomanganese Auxiliary.
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DOI：
10.1021/acs.orglett.5b03681
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发表时间：
2016-03-18
期刊：
影响因子：
5.2
通讯作者：
Lepore SD
中科院分区：
文献类型：
--
作者：
Roy A;Bhat BA;Lepore SD
手性铵盐催化有机锰络合炔醛异构化为手性联烯醛结构单元，具有中等到良好的对映体过量。通常，共辄炔基醛不会异构化成它们的异构性较不稳定的丙二烯异构体。然而，在适当的锰助剂，以促进丙二烯的形成，实现了不对称质子化的cumulenolate中间体使用各种辛可啶盐在弱碱性两相反应体系。最佳的结果是实现了使用一种新的辛可尼丁香叶基衍生物，其C-9羟基在对映体选择性中起着至关重要的作用。
Chiral ammonium salts were used to catalyze the isomerization of organomanganese-complexed alkynyl aldehydes to chiral allenal building blocks in moderate to good enantiomeric excesses. Normally, conjugated alkynyl aldehydes do not isomerize to their thermodynamically less stable allene isomers. However, with a manganese auxiliary in place to promote allene formation, asymmetric protonation of cumulenolate intermediates was realized using a variety of cinchonidinium salts in a weakly basic biphasic reaction system. Optimal results were realized using a novel cinchonidinium geranyl derivative with its C-9 hydroxyl group playing a crucial role in enantioselectivity.
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影响因子：
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