Premium
1,2‐Stereochemical Induction in the Pd II ‐Catalyzed Conjugate Addition of Boronic Acids
Author(s) -
Roscales Silvia,
Sánchez Francisco,
Csákÿ Aurelio G.
Publication year - 2015
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201403488
Subject(s) - chemistry , enantiopure drug , stereoselectivity , substituent , asymmetric induction , boronic acid , conjugate , aldehyde , catalysis , addition reaction , enantioselective synthesis , palladium , stereochemistry , organic chemistry , mathematical analysis , mathematics
Palladium(II) catalysis has been used in the substrate‐controlled 1,2‐chiral induction of the conjugate addition of boronic acids to enantiopure α,β‐unsaturated ketones and esters without competition from the Mirozoki–Heck reaction. Bedford's palladacycle was found to control the stereoselectivity without the need for additional chiral ligands. We report that the Pd II ‐catalyzed conjugate addition reaction between boronic acids and acyclic ketones or esters that bear a hydroxyl substituent at their γ‐position (glyceraldehyde derivatives) can afford high levels of anti stereoselection, comparable to those reported previously using more expensive Rh I catalysts. On the other hand, high levels of syn stereoselectivity were observed with acyclic esters that bear an amino substituent at their γ‐position (serine derivatives). In this case, the levels of stereoselection could be enhanced by using cyclic derivatives derived from Garner's aldehyde.