Reversible nucleophilic addition can lower the observed enantioselectivity in palladium-catalyzed allylic amination reactions with a variety of chiral ligands

Autor:	Madison B. Goodstein, Nathaniel C. Nelson, Michael L Martini, Isabelle N.-M. Leibler, Zitong B. Jia, Bryan Holtzman, Richard C. Bunt, Nicholas S. Caminiti
Rok vydání:	2015
Předmět:	Allylic rearrangement Nucleophilic addition Ligand Organic Chemistry Chiral ligand Enantioselective synthesis Biochemistry Combinatorial chemistry Catalysis chemistry.chemical_compound Benzylamine chemistry Drug Discovery Organic chemistry Amination
Zdroj:	Tetrahedron Letters. 56:5445-5448
ISSN:	0040-4039
DOI:	10.1016/j.tetlet.2015.08.010
Popis:	Palladium-catalyzed allylic amination is an important synthetic reaction that is also frequently used as a benchmark for the design and evaluation of new chiral ligands. The effect of reversible nucleophilic addition on the reaction of benzylamine with ( E )-1,3-diphenylallyl ethyl carbonate ( 1 ) in CH 2 Cl 2 was examined with 12 different chiral ligands across a range of scaffolding types. In 8 out of 12 cases the observed ee was significantly higher when DBU or Cs 2 CO 3 was added to suppress the proton-driven reversibility. For chiral ligand screening with this test reaction, adding DBU or Cs 2 CO 3 provides a better measure of the ligand’s inherent enantioselectivity.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::5431e28f07d82e113f29867254ba821a https://doi.org/10.1016/j.tetlet.2015.08.010 Zobrazit plný text záznamu Full Text from ScienceDirect