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Comparing the Enantioselective Power of Steric and Electrostatic Effects in Transition‐Metal‐Catalyzed Asymmetric Synthesis
Author(s) -
Poater Albert,
Ragone Francesco,
Mariz Ronaldo,
Dorta Reto,
Cavallo Luigi
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201001938
Subject(s) - enantioselective synthesis , steric effects , catalysis , chemistry , transition metal , selectivity , combinatorial chemistry , phenylboronic acid , substrate (aquarium) , asymmetric induction , computational chemistry , organic chemistry , oceanography , geology
The current approach to improve and tune the enantioselective performances of transition‐metal catalysts for asymmetric synthesis is mostly focused to modifications of the steric properties of the ancillary ligands of the active metal. Nevertheless, it is also known that electrostatic effects can have a remarkable role to promote selectivity in asymmetric synthesis. Using the Rh‐catalyzed asymmetric 1,4‐addition of phenylboronic acid to 2‐cyclohexenone leading to chiral 3‐phenylcyclohexanone as an example, we could show that high enantioselectivity can be indeed achieved using catalysts essentially based either on steric or electrostatic effects as the main source of enantioselective induction. In this contribution we suggest that the analysis of the surface of interaction between the catalyst and the substrate could be a useful tool to quantify the power of steric and electrostatic effects of catalysts.