Rh-Catalyzed Desymmetrization of α-Quaternary Centers by Isomerization-Hydroacylation.
Rh-Catalyzed Desymmetrization of α-Quaternary Centers by Isomerization-Hydroacylation.
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DOI：
10.1039/c5sc01553g
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发表时间：
2015-08-01
期刊：
影响因子：
8.4
通讯作者：
Dong VM
中科院分区：
文献类型：
--
作者：
Park JW;Kou KG;Kim DK;Dong VM
在Rh催化下，α，α-双(烯丙基)醛通过对映选择性异构化和烯烃导向的氢酰化反应进行去对称化反应。我们描述了Rh催化的α，α-双(烯丙基)醛通过级联异构化和氢酰化反应的全碳四元中心的脱对称反应。这种去对称化与另外两种由C-H键激活引发的新型烯烃官能化竞争，包括碳酰化和双酰化。BIPHEP配体促进α-乙烯基环戊酮的对映选择性形成。机理研究支持不可逆和对映选择性的烯烃异构化反应，然后是烯烃氢酰化反应。
A Rh-catalyzed desymmetrization of α,α-bis(allyl)aldehydes occurs by enantioselective isomerization followed by olefin-directed hydroacylation. We describe a Rh-catalyzed desymmetrization of all-carbon quaternary centers from α,α-bis(allyl)aldehydes by a cascade featuring isomerization and hydroacylation. This desymmetrization competes with two other novel olefin functionalizations that are triggered by C–H bond activation, including carboacylation and bisacylation. A BIPHEP ligand promotes enantioselective formation of α-vinylcyclopentanones. Mechanistic studies support irreversible and enantioselective olefin-isomerization followed by olefin-hydroacylation.