Redox-Noninnocent Ligand-Supported Vanadium Catalysts for the Chemoselective Reduction of C=X (X = O, N) Functionalities

Zhang, Guoqi; Wu, Jing; Zheng, Shengping; Neary, Michelle C.; Mao, Jincheng; Flores, Marco; Trovitch, Ryan J.; Dub, Pavel A.

doi:10.1021/jacs.9b07062

Title: Redox-Noninnocent Ligand-Supported Vanadium Catalysts for the Chemoselective Reduction of C=X (X = O, N) Functionalities

Journal Article · Tue Sep 03 00:00:00 EDT 2019 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.9b07062· OSTI ID:1570623

^[1]; Wu, Jing ^[2];

^[3];

^[4];

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^[6]

The Graduate Center of City Univ. of New York, New York, NY (United States)
The Graduate Center of City Univ. of New York, New York, NY (United States); City Univ. of New York, New York, NY (United States)
City Univ. of New York, New York, NY (United States)
Southwest Petroleum Univ., Sichuan (People’s Republic of China)
Arizona State Univ., Tempe, AZ (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Catalysis is the second largest application for V after its use as an additive to improve steel production. Molecular complexes of vanadium(V) are particularly useful and efficient catalysts for oxidation processes; however, their ability to catalyze reductive transformations has yet to be fully explored. Here we report the first examples of polar organic functionality reduction mediated by V. Open-shell V^III complexes that feature a π-radical monoanionic 2,2':6',2"-terpyridine ligand (Rtpy^•)^– functionalized at the 4'-position (R = (CH₃)₃SiCH₂, C₆H₅) catalyze mild and chemoselective hydroboration and hydrosilylation of functionalized ketones, aldehydes, imines, esters, and carboxamides with turnover numbers (TONs) of up to ~1000 and turnover frequencies (TOFs) of up to ~500 h^–1. In conclusion, computational evaluation of the precatalyst synthesis and activation has revealed underappreciated complexity associated with the redox-active tpy chelate.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 1570623

Report Number(s):: LA-UR-19-22935

Journal Information:: Journal of the American Chemical Society, Vol. 141, Issue 38; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 56 works

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References (57)

The role of the metal-bound N–H functionality in Noyori-type molecular catalysts Dub, Pavel A.; Gordon, John C. Nature Reviews Chemistry, Vol. 2, Issue 12 https://doi.org/10.1038/s41570-018-0049-z	journal	November 2018
Metal–Ligand Bifunctional Catalysis: The “Accepted” Mechanism, the Issue of Concertedness, and the Function of the Ligand in Catalytic Cycles Involving Hydrogen Atoms Dub, Pavel A.; Gordon, John C. ACS Catalysis, Vol. 7, Issue 10 https://doi.org/10.1021/acscatal.7b01791	journal	September 2017
Non-innocent ligands Berben, Louise A.; de Bruin, Bas; Heyduk, Alan F. Chemical Communications, Vol. 51, Issue 9 https://doi.org/10.1039/C4CC90480J	journal	January 2015
Redox-active ligands in catalysis Luca, Oana R.; Crabtree, Robert H. Chem. Soc. Rev., Vol. 42, Issue 4 https://doi.org/10.1039/C2CS35228A	journal	January 2013
Redox Non-Innocent Ligands: Versatile New Tools to Control Catalytic Reactions Lyaskovskyy, Volodymyr; de Bruin, Bas ACS Catalysis, Vol. 2, Issue 2 https://doi.org/10.1021/cs200660v	journal	January 2012
Systematics and Future Projections Concerning Redox-Noninnocent Amide/Imine Ligands Caulton, Kenneth G. European Journal of Inorganic Chemistry, Vol. 2012, Issue 3 https://doi.org/10.1002/ejic.201100623	journal	November 2011
Cooperative & Redox Non-Innocent Ligands in Directing Organometallic Reactivity (Eur. J. Inorg. Chem. 3/2012) Hindson, Karen; de Bruin, Bas European Journal of Inorganic Chemistry, Vol. 2012, Issue 3 https://doi.org/10.1002/ejic.201290001	journal	January 2012
Preface: Forum on Redox-Active Ligands Chirik, Paul J. Inorganic Chemistry, Vol. 50, Issue 20 https://doi.org/10.1021/ic201881k	journal	October 2011
Radical Ligands Confer Nobility on Base-Metal Catalysts Chirik, P. J.; Wieghardt, K. Science, Vol. 327, Issue 5967 https://doi.org/10.1126/science.1183281	journal	February 2010
Metal complexes with non-innocent ligands Butin, Kim P.; Beloglazkina, Elena K.; Zyk, Nikolai V. Russian Chemical Reviews, Vol. 74, Issue 6 https://doi.org/10.1070/RC2005v074n06ABEH000977	journal	June 2005
Carbon-Carbon Bond Formation in a Weak Ligand Field: Leveraging Open-Shell First-Row Transition-Metal Catalysts Chirik, Paul J. Angewandte Chemie International Edition, Vol. 56, Issue 19 https://doi.org/10.1002/anie.201611959	journal	March 2017
Catalytic Applications of Vanadium: A Mechanistic Perspective Langeslay, Ryan R.; Kaphan, David M.; Marshall, Christopher L. Chemical Reviews, Vol. 119, Issue 4 https://doi.org/10.1021/acs.chemrev.8b00245	journal	October 2018
Vanadium complexes: Recent progress in oxidation catalysis Sutradhar, Manas; Martins, Luísa M. D. R. S.; Guedes da Silva, M. Fátima C. Coordination Chemistry Reviews, Vol. 301-302 https://doi.org/10.1016/j.ccr.2015.01.020	journal	October 2015
Design of Vanadium Complex Catalysts for Precise Olefin Polymerization Nomura, Kotohiro; Zhang, Shu Chemical Reviews, Vol. 111, Issue 3 https://doi.org/10.1021/cr100207h	journal	March 2011
Z -Selective Semihydrogenation of Alkynes Catalyzed by a Cationic Vanadium Bisimido Complex La Pierre, Henry S.; Arnold, John; Toste, F. Dean Angewandte Chemie International Edition, Vol. 50, Issue 17 https://doi.org/10.1002/anie.201007876	journal	March 2011
Oxidative Addition of a Dinuclear and Divalent Vanadium Hydride to an Olefin C−H Bond, Leading to Catalytic Hydrogenation Aharonian, Ghazar; Gambarotta, Sandro; Yap, Glenn P. A. Organometallics, Vol. 20, Issue 24 https://doi.org/10.1021/om010707+	journal	October 2001
Catalytic hydrogenation of olefins with the VCl4−Mg−H2 system in tetrahydrofuran Sobota, P.; Jeżowska-Trzebiatowska, B.; Utko, J. Reaction Kinetics and Catalysis Letters, Vol. 4, Issue 1 https://doi.org/10.1007/BF02073979	journal	March 1976
Redox-Active Ligands and Organic Radical Chemistry Zhu, Di; Thapa, Indira; Korobkov, Ilia Inorganic Chemistry, Vol. 50, Issue 20 https://doi.org/10.1021/ic2002145	journal	October 2011
Highly Selective Hydroboration of Alkenes, Ketones and Aldehydes Catalyzed by a Well-Defined Manganese Complex Zhang, Guoqi; Zeng, Haisu; Wu, Jing Angewandte Chemie International Edition, Vol. 55, Issue 46 https://doi.org/10.1002/anie.201607579	journal	October 2016
Dearomatization and Functionalization of Terpyridine Ligands Leading to Unprecedented Zwitterionic Meisenheimer Aluminum Complexes and Their Use in Catalytic Hydroboration Zhang, Guoqi; Wu, Jing; Zeng, Haisu ACS Catalysis, Vol. 9, Issue 2 https://doi.org/10.1021/acscatal.8b04096	journal	December 2018
Neutral Bis(imino)-1,4-dihydropyridinate and Cationic Bis(imino)pyridine σ-Alkylzinc(II) Complexes as Hydride Exchange Systems: Classic Organometallic Chemistry Meets Ligand-Centered, Biomimetic Reactivity Sandoval, John J.; Álvarez, Eleuterio; Palma, Pilar Organometallics, Vol. 37, Issue 11 https://doi.org/10.1021/acs.organomet.8b00183	journal	May 2018
Mechanism of Alkyl Migration in Diorganomagnesium 2,6-Bis(imino)pyridine Complexes: Formation of Grignard-Type Complexes with Square-Planar Mg(II) Centers Sandoval, John J.; Palma, Pilar; Álvarez, Eleuterio Organometallics, Vol. 35, Issue 18 https://doi.org/10.1021/acs.organomet.6b00528	journal	September 2016
Radical Chemistry of Iminepyridine Ligands Budzelaar, Peter H. M. European Journal of Inorganic Chemistry, Vol. 2012, Issue 3 https://doi.org/10.1002/ejic.201100698	journal	September 2011
Selective Alkylation of 2,6-Diiminopyridine Ligands by Dialkylmanganese Reagents: A “One-Pot” Synthetic Methodology Cámpora, Juan; Pérez, Carmen M.; Rodríguez-Delgado, Antonio Organometallics, Vol. 26, Issue 4 https://doi.org/10.1021/om0609517	journal	February 2007
Ligand-centred reactivity in diiminepyridine complexes Knijnenburg, Quinten; Gambarotta, Sandro; Budzelaar, Peter H. M. Dalton Transactions, Issue 46 https://doi.org/10.1039/b612251e	journal	January 2006
High-Activity Cobalt Catalysts for Alkene Hydroboration with Electronically Responsive Terpyridine and α-Diimine Ligands Palmer, W. Neil; Diao, Tianning; Pappas, Iraklis ACS Catalysis, Vol. 5, Issue 2 https://doi.org/10.1021/cs501639r	journal	December 2014
Experimental Fingerprints for Redox-Active Terpyridine in [Cr(tpy) ₂ ](PF ₆ ) _n ( n = 3–0), and the Remarkable Electronic Structure of [Cr(tpy) ₂ ] ^1– Scarborough, Christopher C.; Lancaster, Kyle M.; DeBeer, Serena Inorganic Chemistry, Vol. 51, Issue 6 https://doi.org/10.1021/ic2027219	journal	March 2012
Ligand Redox Effects in the Synthesis, Electronic Structure, and Reactivity of an Alkyl−Alkyl Cross-Coupling Catalyst Jones, Gavin D.; Martin, Jason L.; McFarland, Chris Journal of the American Chemical Society, Vol. 128, Issue 40 https://doi.org/10.1021/ja063334i	journal	October 2006
Evidence for a Ni ^I Active Species in the Catalytic Cross-Coupling of Alkyl Electrophiles Anderson, Thomas J.; Jones, Gavin D.; Vicic, David A. Journal of the American Chemical Society, Vol. 126, Issue 26 https://doi.org/10.1021/ja0483903	journal	July 2004
High-frequency and -field electron paramagnetic resonance of vanadium(IV, III, and II) complexes Krzystek, J.; Ozarowski, Andrew; Telser, Joshua Coordination Chemistry Reviews, Vol. 301-302 https://doi.org/10.1016/j.ccr.2014.10.014	journal	October 2015
Vanadocene de Novo : Spectroscopic and Computational Analysis of Bis(η ⁵ -cyclopentadienyl)vanadium(II) Jackson, Timothy A.; Krzystek, J.; Ozarowski, Andrew Organometallics, Vol. 31, Issue 23 https://doi.org/10.1021/om300892y	journal	November 2012
New Homoleptic Organometallic Derivatives of Vanadium(III) and Vanadium(IV): Synthesis, Characterization, and Study of Their Electrochemical Behaviour Alonso, Pablo J.; Forniés, Juan; García-Monforte, M. Angeles Chemistry - A European Journal, Vol. 11, Issue 16 https://doi.org/10.1002/chem.200401190	journal	August 2005
Effective exchange integrals for open-shell species by density functional methods Yamanaka, S.; Kawakami, T.; Nagao, H. Chemical Physics Letters, Vol. 231, Issue 1 https://doi.org/10.1016/0009-2614(94)01221-0	journal	December 1994
A spin correction procedure for unrestricted Hartree-Fock and Møller-Plesset wavefunctions for singlet diradicals and polyradicals Yamaguchi, K.; Jensen, F.; Dorigo, A. Chemical Physics Letters, Vol. 149, Issue 5-6 https://doi.org/10.1016/0009-2614(88)80378-6	journal	September 1988
New Possibilities for Magnetic Control of Chemical and Biochemical Reactions Buchachenko, Anatoly; Lawler, Ronald G. Accounts of Chemical Research, Vol. 50, Issue 4 https://doi.org/10.1021/acs.accounts.6b00608	journal	February 2017
KO t Bu: A Privileged Reagent for Electron Transfer Reactions? Barham, Joshua P.; Coulthard, Graeme; Emery, Katie J. Journal of the American Chemical Society, Vol. 138, Issue 23 https://doi.org/10.1021/jacs.6b03282	journal	May 2016
Large-Scale Carbonyl Reductions in the Pharmaceutical Industry Magano, Javier; Dunetz, Joshua R. Organic Process Research & Development, Vol. 16, Issue 6 https://doi.org/10.1021/op2003826	journal	April 2012
Catalytic Reductive Transformations of Carboxylic and Carbonic Acid Derivatives Using Molecular Hydrogen Dub, Pavel A.; Ikariya, Takao ACS Catalysis, Vol. 2, Issue 8 https://doi.org/10.1021/cs300341g	journal	July 2012
Highlights of Transition Metal-Catalyzed Asymmetric Hydrogenation of Imines Fleury-Brégeot, Nicolas; de la Fuente, Verónica; Castillón, Sergio ChemCatChem, Vol. 2, Issue 11 https://doi.org/10.1002/cctc.201000078	journal	August 2010
Recent topics in catalytic asymmetric hydrogenation of ketones Yoshimura, Masahiro; Tanaka, Shinji; Kitamura, Masato Tetrahedron Letters, Vol. 55, Issue 27 https://doi.org/10.1016/j.tetlet.2014.04.129	journal	July 2014
Catalytic Hydroboration of Carbonyl Derivatives, Imines, and Carbon Dioxide Chong, Che Chang; Kinjo, Rei ACS Catalysis, Vol. 5, Issue 6 https://doi.org/10.1021/acscatal.5b00428	journal	April 2015
Mechanistic Investigation of Bis(imino)pyridine Manganese Catalyzed Carbonyl and Carboxylate Hydrosilylation Mukhopadhyay, Tufan K.; Rock, Christopher L.; Hong, Mannkyu Journal of the American Chemical Society, Vol. 139, Issue 13 https://doi.org/10.1021/jacs.7b00879	journal	March 2017
Chemoselective reduction of carboxamides Volkov, Alexey; Tinnis, Fredrik; Slagbrand, Tove Chemical Society Reviews, Vol. 45, Issue 24 https://doi.org/10.1039/C6CS00244G	journal	January 2016
POCN Ni( ii ) pincer complexes: synthesis, characterization and evaluation of catalytic hydrosilylation and hydroboration activities Gudun, Kristina A.; Segizbayev, Medet; Adamov, Assyl Dalton Transactions, Vol. 48, Issue 5 https://doi.org/10.1039/C8DT04854A	journal	January 2019
A Manganese Pre-Catalyst: Mild Reduction of Amides, Ketones, Aldehydes, and Esters Kelly, Colin M.; McDonald, Robert; Sydora, Orson L. Angewandte Chemie International Edition, Vol. 56, Issue 50 https://doi.org/10.1002/anie.201709441	journal	November 2017
Magnesium amide catalyzed selective hydroboration of esters Barman, Milan Kr.; Baishya, Ashim; Nembenna, Sharanappa Dalton Transactions, Vol. 46, Issue 13 https://doi.org/10.1039/C7DT00556C	journal	January 2017
Magnesium-catalyzed hydroboration of esters: evidence for a new zwitterionic mechanism Mukherjee, Debabrata; Ellern, Arkady; Sadow, Aaron D. Chem. Sci., Vol. 5, Issue 3 https://doi.org/10.1039/C3SC52793J	journal	January 2014
Catalytic hydroboration by an imido-hydrido complex of Mo( iv ) Khalimon, Andrey Y.; Farha, Philip; Kuzmina, Lyudmila G. Chem. Commun., Vol. 48, Issue 3 https://doi.org/10.1039/C1CC14508H	journal	January 2012
Magnesium-Catalyzed Hydroboration of Pyridines Arrowsmith, Merle; Hill, Michael S.; Hadlington, Terrance Organometallics, Vol. 30, Issue 21 https://doi.org/10.1021/om2008138	journal	November 2011
Bench-Stable Cobalt Pre-Catalysts for Mild Hydrosilative Reduction of Tertiary Amides to Amines and Beyond Nurseiit, Alibek; Janabel, Jaysan; Gudun, Kristina A. ChemCatChem, Vol. 11, Issue 2 https://doi.org/10.1002/cctc.201801605	journal	January 2019
A comparative analysis of hydrosilative amide reduction catalyzed by first-row transition metal (Mn, Fe, Co, and Ni) N -phosphinoamidinate complexes Macaulay, Casper M.; Ogawa, Takahiko; McDonald, Robert Dalton Transactions, Vol. 48, Issue 26 https://doi.org/10.1039/C8DT04221G	journal	January 2019
Magnesium-Catalyzed Mild Reduction of Tertiary and Secondary Amides to Amines Lampland, Nicole L.; Hovey, Megan; Mukherjee, Debabrata ACS Catalysis, Vol. 5, Issue 7 https://doi.org/10.1021/acscatal.5b01038	journal	June 2015
Well-Defined Cyclopentadienyl NHC Iron Complex as the Catalyst for Efficient Hydrosilylation of Amides to Amines and Nitriles Bézier, David; Venkanna, Gopaladasu T.; Sortais, Jean-Baptiste ChemCatChem, Vol. 3, Issue 11 https://doi.org/10.1002/cctc.201100202	journal	August 2011
New catalytic properties of iron complexes: dehydration of amides to nitriles Zhou, Shaolin; Addis, Daniele; Das, Shoubhik Chemical Communications, Issue 32 https://doi.org/10.1039/b910145d	journal	January 2009
Functionalization of Tetraorganosilanes and Permethyloligosilanes at a Methyl Group on Silicon via Iridium-Catalyzed C(sp ³ )–H Borylation Ohmura, Toshimichi; Torigoe, Takeru; Suginome, Michinori Organometallics, Vol. 32, Issue 21 https://doi.org/10.1021/om400900z	journal	October 2013
Addition of Metalloid Hydrides to Alkynes: Hydrometallation with Boron, Silicon, and Tin Trost, Barry M.; Ball, Zachary T. Synthesis, Vol. 2005, Issue 06 https://doi.org/10.1055/s-2005-861874	journal	January 2005
Iron-Catalyzed Hydroboration: Unlocking Reactivity through Ligand Modulation Espinal-Viguri, Maialen; Woof, Callum R.; Webster, Ruth L. Chemistry - A European Journal, Vol. 22, Issue 33 https://doi.org/10.1002/chem.201602818	journal	July 2016

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