Enantioselective Synthesis of Vicinal All-Carbon Quaternary Centers via Iridium-Catalyzed Allylic Alkylation.
Enantioselective Synthesis of Vicinal All-Carbon Quaternary Centers via Iridium-Catalyzed Allylic Alkylation.
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DOI：
10.1002/anie.201804820
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发表时间：
2018-07-09
期刊：
影响因子：
--
通讯作者：
Stoltz BM
中科院分区：
文献类型：
--
作者：
Hethcox JC;Shockley SE;Stoltz BM
公开了第一种对映选择性过渡金属催化的烯丙基烷基化的发展，提供了获得邻近全碳季中心的无环产品的途径。铱催化的烯丙基烷基化反应对一系列丙二腈衍生的亲核试剂和三取代的烯丙基亲电试剂具有优异的收率和选择性。通过一系列不同的化学和非对映选择性产物转化，探索了这些立体拥挤产物的效用，以提供许多高价值的、密集功能化的构建块，包括那些含有邻全碳季立体中心的构建块。开发了第一个对映选择性过渡金属催化的烯丙基烷基化反应，提供了获得邻全碳季中心的无环产物的途径。铱催化的反应对一系列丙二腈衍生的亲核试剂和三取代的烯丙基亲电试剂具有优异的产率和选择性。通过一系列不同的化学选择性和非对映选择性产物转化，探索这些立体拥挤产物的效用，以提供许多高价值的、密集功能化的构建块，包括那些含有邻全碳季立体中心的构建块。
The development of the first enantioselective transition metal-catalyzed allylic alkylation providing access to acyclic products bearing vicinal all-carbon quaternary centers is disclosed. The iridium-catalyzed allylic alkylation reaction proceeds with excellent yields and selectivities for a range of malononitrile-derived nucleophiles and trisubstituted allylic electrophiles. The utility of these sterically congested products is explored through a series of diverse chemo- and diastereoselective product transformations to afford a number of highly valuable, densely functionalized building blocks, including those containing vicinal all-carbon quaternary stereocenters. The first enantioselective transition metal-catalyzed allylic alkylation providing access to acyclic products bearing vicinal all-carbon quaternary centers has been developed. The iridium-catalyzed reaction proceeds with excellent yields and selectivities for a range of malononitrile-derived nucleophiles and trisubstituted allylic electrophiles. The utility of these sterically congested products is explored through a series of diverse chemoselective and diastereoselective product transformations to afford a number of highly valuable, densely functionalized building blocks, including those containing vicinal all-carbon quaternary stereocenters.
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