Cp2ZrMeCl: A Reagent for Asymmetric Methyl Addition.
Cp2ZrMeCl: A Reagent for Asymmetric Methyl Addition.
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DOI：
10.1021/acs.orglett.6b01829
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发表时间：
2016-07
期刊：
影响因子：
5.2
通讯作者：
Kilian Garrec;S. Fletcher
中科院分区：
文献类型：
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作者：
Kilian Garrec;S. Fletcher
描述了Cp2ZrMeCl作为不对称催化中亲核甲基的来源。这种容易制备的试剂是稳定的，可在空气中称重，通常在室温下用于高对映选择性铜催化加成反应。甲基被成功地（通常为bbb90 % ee）添加到环和非环α，β-不饱和酮的1,4-加成物中，形成叔中心和季中心。还报道了催化剂控制非对映选择性1,6加成反应和动态动力学不对称烯丙基烷基化反应的例子。该试剂用于催化不对称合成天然香味(R)-(-)-麝香（82%产率，91% ee）。
The use of Cp2ZrMeCl is described as a source of nucleophilic methyl in asymmetric catalysis. This easily prepared reagent is bench stable, weighable in air, and generally useful in highly enantioselective copper-catalyzed addition reactions at room temperature. Methyl is successfully (generally >90% ee) added in 1,4-additions to cyclic and acyclic α,β-unsaturated ketones to provide tertiary and quaternary centers. Examples of catalyst controlled diastereoselective 1,6-addition and dynamic kinetic asymmetric allylic alkylation reactions are also reported. The reagent is used in the catalytic asymmetric synthesis of naturally occurring fragrance (R)-(-)-muscone (82% yield, 91% ee).