Abstract:
A new general method of controlling the chemical reactivity of molecules is proposed. Instead of tuning the electronic properties of reactive molecules by employing functional groups that impose different inductive effects to a molecule, we propose to immobilize the parent molecule onto an electrode, for example by installing a thiol group to the molecule and forming a self-assembled monolayer on a gold surface. By applying a voltage the electronic property of the immobilized molecule can be tuned, as is commonly done by decorating the molecule with electron-donating and electron-withdrawing groups. As a proof of principle, it is shown that the base-catalyzed saponification of benzoic ester can be shut down completely by applying a negative voltage, while it can be accelerated by using a positive voltage. Furthermore it is shown that the Suzuki-Miyaura cross-coupling reaction can be affected by the voltage when the arylhalide substrate of the reaction is immobilized on a gold electrode.
Bigraphy:
EDUCATION
B.Sc. Heinrich-Heine-University Düsseldorf, Germany, 1990-1994
Ph. D. Univ. of North Carolina Chapel Hill, 1994-2000
Postdoctoral Fellow Columbia University, USA, 2000-2003
ACADEMIC CAREER
2003-2015, Assistant and tenured Associate Professor, Indiana Univ. Bloomington
2015-present, Associate Director, CCHF-IBS and Professor, KAIST
RESEARCH INTERESTS
Computational Chemistry, Reaction Mechanisms, Electronic Structure, Transition Metal Catalyzed Reactions
SELECTED PUBLICATIONS
[1] “Selective Formation of γ-lactams via C−H Amidation Enabled by Tailored Iridium Catalysts” Seung Youn Hong,
Yoonsu Park, Yeongyu Hwang, Yeong Bum Kim, Mu-Hyun Baik and Sukbok Chang, Science 2018, 359, 1016-1021
[2] “Catalytic Borylation of Methane” Kyle T. Smith, Simon Berritt, Mariano Gonzalez, Seihwan Ahn, Milton R.
Smith III, Mu-Hyun Baik and Daniel J. Mindiola, Science 2016, 351, 1424-1427
[3] “Iridium-catalysed arylation of C–H bonds enabled by oxidatively induced reductive elimination” Kwangmin
Shin, Yoonsu Park, Mu-Hyun Baik and Sukbok Chang, Nat. Chem. 2018, 10, 218-224
[4] “The Mechanism of Rh-Catalyzed Oxidative Cyclizations: Closed vs. Open Shell Pathways” Yoonsu Park, Seihwan
Ahn, Dahye Kang and Mu-Hyun Baik, Acc. Chem. Res. 2016, 49, 1263-1270
[5] “A new and selective cycle for dehydrogenation of linear and cyclic alkanes under mild conditions using a base
metal” Douglas P. Solowey, Manoj V. Mane, Takashi Kurogi, Patrick J. Carroll, Brian C. Manor, Mu-Hyun Baik and
Daniel J. Mindiola, Nat. Chem. 2017, 9, 1126-1132