Promoting Highly Diastereoselective γ-C-H Chalcogenation of α-Amino Acids and Aliphatic Carboxylic Acids
Promoting Highly Diastereoselective γ-C-H Chalcogenation of α-Amino Acids and Aliphatic Carboxylic Acids
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DOI：
10.1021/acscatal.7b04074
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发表时间：
2018-04-01
期刊：
影响因子：
12.9
通讯作者：
Maiti, Debabrata
中科院分区：
文献类型：
--
作者：
Guin, Srimanta;Deb, Arghya;Maiti, Debabrata
已经证明了Pd（II）催化的脂肪族羧酸的高度区域选择性的γ-硫族化、硫代芳基化和硒代芳基化。本方案提供了以高非对映选择性（高达52：1）对氨基酸如缬氨酸、异亮氨酸和叔亮氨酸进行结构修饰的直接途径。已经在γ-sp（3）C-Hs上进行了连续的异双官能化，导致四元中心的去对称化。硫族化产物的应用潜力表现为使用它们作为合成生物相关的苯并硫杂环庚酮部分的前体。进行了初步研究，以深入了解该机制。
A Pd(II)-catalyzed highly regioselective gamma-chalcogenation, thioarylation, and selenoarylation of aliphatic carboxylic acids has been demonstrated. The present protocol provides a direct access to make structural modifications of a amino acids such as valine, isoleucine, and tert-leucine with high diastereoselectivity (up to 52:1). Sequential hetero-bifunctionalizations have been carried out at gamma-sp(3) C-Hs, resulting in desymmetrization of quaternary centers. The applicative potential of the chalcogenated products was exhibited by using them as precursors for the synthesis of the biologically relevant benzothiepinone moiety. Preliminary studies were carried out to gain insights into the mechanism.