钯催化环戊酮的对映选择性脱羧烯丙基烷基化反应
Palladium-Catalyzed Enantioselective Decarboxylative Allylic Alkylation of Cyclopentanones.
作者信息
Craig Robert A, Loskot Steven A, Mohr Justin T, Behenna Douglas C, Harned Andrew M, Stoltz Brian M
机构信息
Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering Division of Chemistry and Chemical Engineering, California Institute of Technology , MC 101-20, Pasadena, California 91125, United States.
出版信息
Org Lett. 2015 Nov 6;17(21):5160-3. doi: 10.1021/acs.orglett.5b02376. Epub 2015 Oct 26.
The first general method for the enantioselective construction of all-carbon quaternary centers on cyclopentanones by enantioselective palladium-catalyzed decarboxylative allylic alkylation is described. Employing the electronically modified (S)-(p-CF3)3-t-BuPHOX ligand, α-quaternary cyclopentanones were isolated in yields up to >99% with ee's up to 94%. Additionally, in order to facilitate large-scale application of this method, a low catalyst loading protocol was employed, using as little as 0.15 mol % Pd, furnishing the product without any loss in ee.
本文描述了通过对映选择性钯催化的脱羧烯丙基烷基化反应，对环戊酮上的全碳季碳中心进行对映选择性构建的首个通用方法。使用电子修饰的(S)-(p-CF3)3-t-BuPHOX配体，可分离得到α-季碳环戊酮，产率高达>99%，对映体过量值（ee）高达94%。此外，为便于该方法的大规模应用，采用了低催化剂负载方案，仅使用低至0.15 mol%的钯，产物的对映体过量值没有任何损失。
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