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Ligand‐Controlled Regiodivergent Pathways of Rhodium(III)‐Catalyzed Dihydroisoquinolone Synthesis: Experimental and Computational Studies of Different Cyclopentadienyl Ligands
Author(s) -
Wodrich Matthew D.,
Ye Baihua,
Gonthier Jérôme F.,
Corminboeuf Clémence,
Cramer Nicolai
Publication year - 2014
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.201404515
Subject(s) - regioselectivity , rhodium , chemistry , ligand (biochemistry) , catalysis , aryl , density functional theory , combinatorial chemistry , adduct , stereochemistry , cyclopentadienyl complex , transition state , acceptor , computational chemistry , organic chemistry , alkyl , receptor , biochemistry , physics , condensed matter physics
Rh III ‐catalyzed directed CH functionalizations of arylhydroxamates have become a valuable synthetic tool. To date, the regioselectivity of the insertion of the unsaturated acceptor into the common cyclometalated intermediate was dependent solely on intrinsic substrate control. Herein, we report two different catalytic systems that allow the selective formation of regioisomeric 3‐aryl dihydroisoquinolones and previously inaccessible 4‐aryl dihydroisoquinolones under full catalyst control. The differences in the catalysts are computationally examined using density functional theory and transition state theory of different possible pathways to elucidate key contributing factors leading to the regioisomeric products. The stabilities of the initially formed rhodium complex styrene adducts, as well as activation barrier differences for the migratory insertion, were identified as key contributing factors for the regiodivergent pathways.