期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 28, 期 24, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202200273
关键词
allylic substitution; asymmetric desymmetrization; bimetallic catalysis; branched selectivity; geminal dicarboxylate
资金
- National Natural Science Foundation of China [21831005, 21901158, 22171183]
- Shanghai Sailing Program [19YF1421900]
Asymmetric desymmetrization is a powerful strategy for building stereocenters in asymmetric synthesis. This study reports a Pd/Cu catalyzed asymmetric desymmetrization reaction using a simple geminal dicarboxylate, which achieved good yields and high selectivity.
Asymmetric desymmetrization has been demonstrated to be a powerful strategy for building stereocenters in asymmetric synthesis. Herein, a Pd/Cu catalyzed asymmetric desymmetrization reaction with a simple geminal dicarboxylate is reported. A wide scope of imino esters bearing an aryl or heteroaromatic group were compatible with this bimetallic catalytic system. The reactions proceeded smoothly, giving the desired products in good yields with high to excellent regio-, diastereo-, and enantioselectivity (up to 20 : 1 branched:linear, >20 : 1 dr, >99 % ee). Notably, the reaction favored branched selectivity, which is unusual for the Pd-catalyzed allylic alkylation reaction. In addition, the standard product could be easily transformed to other valuable molecules such as chiral allylic alcohols, carbamates, and organic boron compounds. Furthermore, DFT calculations were conducted to explain the origin of the branched selectivity.
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