Efficient Chemoselective Reduction of N ‐Oxides and Sulfoxides Using a Carbon‐Supported Molybdenum‐Dioxo Catalyst and Alcohol

Li, Jiaqi; Liu, Shengsi; Lohr, Tracy L.; Marks, Tobin J.

doi:10.1002/cctc.201900436

Title: Efficient Chemoselective Reduction of N ‐Oxides and Sulfoxides Using a Carbon‐Supported Molybdenum‐Dioxo Catalyst and Alcohol

Journal Article · Wed May 15 00:00:00 EDT 2019 · ChemCatChem

DOI:https://doi.org/10.1002/cctc.201900436· OSTI ID:1512828

Li, Jiaqi ^[1]; Liu, Shengsi ^[1];

^[2]; Marks, Tobin J. ^[1]

Department of Chemistry Northwestern University 2145 Sheridan Road, Evanston Illinois 60208 USA
Department of Chemistry Northwestern University 2145 Sheridan Road, Evanston Illinois 60208 USA, Current Address Shell Catalysts &, Technologies Shell Technology Center Houston 3333 Highway 6 South Houston Texas 77082 USA

Abstract The chemoselective reduction of a wide range of N ‐oxides and sulfoxides with alcohols is achieved using a carbon‐supported dioxo‐molybdenum ( Mo@C ) catalyst. Of the 10 alcohols screened, benzyl alcohol exhibits the highest reduction efficiency. A variety of N ‐oxide and both aromatic and aliphatic sulfoxide substrates bearing halogens as well as additional reducible functionalities are efficiently and chemoselectively reduced with benzyl alcohol. Chemoselective N ‐oxide reduction is effected even in the presence of potentially competing sulfoxide moieties. In addition, the Mo@C catalyst is air‐ and moisture‐stable, and is easily separated from the reaction mixture and then re‐subjected to reaction conditions over multiple cycles without significant reactivity or selectivity degradation. The high stability and recyclability of the catalyst, paired with its low toxicity and use of earth‐abundant elements makes it an environmentally friendly catalytic system.

View Accepted Manuscript (Publisher)

Cite

Export

Save

Sponsoring Organization:: USDOE

OSTI ID:: 1512828

Journal Information:: ChemCatChem, Journal Name: ChemCatChem Vol. 11 Journal Issue: 16; ISSN 1867-3880

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

Citation Metrics:

Cited by: 12 works

Citation information provided by
Web of Science

References (61)

XLV.—Benzyl sulphoxide: a possible example of dynamic isomerism Smythe, John Armstrong J. Chem. Soc., Trans., Vol. 95, Issue 0 https://doi.org/10.1039/ct9099500349	journal	January 1909
Catalytic 1,2-Regioselective Dearomatization of N-Heteroaromatics via a Hydroboration Liu, Heng; Khononov, Maxim; Eisen, Moris S. ACS Catalysis, Vol. 8, Issue 4 https://doi.org/10.1021/acscatal.8b00074	journal	March 2018
Catalytic Deoxygenation of Sulfoxides by Molecular Hydrogen and its Application to the Homologation of Aromatic Aldehydes Ogura, K.; Yamashita, M.; Tsuchihashi, G. Synthesis, Vol. 1975, Issue 06 https://doi.org/10.1055/s-1975-23763	journal	January 1975
Definition of green synthetic tools based on safer reaction media, heterogeneous catalysis, and flow technology Vaccaro, Luigi; Curini, Massimo; Ferlin, Francesco Pure and Applied Chemistry, Vol. 90, Issue 1 https://doi.org/10.1515/pac-2017-0409	journal	January 2018
Handbook of Heterogeneous Catalysis https://doi.org/10.1002/9783527610044	book	March 2008
Pinacol as a New Green Reducing Agent: Molybdenum- Catalyzed Chemoselective Reduction of Sulfoxides and Nitroaromatics García, Nuria; García-García, Patricia; Fernández-Rodríguez, Manuel A. Advanced Synthesis & Catalysis, Vol. 354, Issue 2-3 https://doi.org/10.1002/adsc.201100877	journal	January 2012
A Study of Acetaldehyde Adsorption on Activated Carbons El-Sayed, Yehya; Bandosz, Teresa J. Journal of Colloid and Interface Science, Vol. 242, Issue 1 https://doi.org/10.1006/jcis.2001.7772	journal	October 2001
Racemization of sulphoxides with halide ions anchimerically assisted by a carboxy-group. The different behaviour of chloride and bromide ions Landini, Dario; Maia, Angela Maria; Rolla, Franco Journal of the Chemical Society, Perkin Transactions 2, Issue 12 https://doi.org/10.1039/p29760001288	journal	January 1976
A noble-metal free Cu-catalyst derived from hydrotalcite for highly efficient hydrogenation of biomass-derived furfural and levulinic acid Yan, Kai; Liao, Jiayou; Wu, Xu RSC Advances, Vol. 3, Issue 12 https://doi.org/10.1039/c3ra22158j	journal	January 2013
Reduction of sulfoxides with boranes catalyzed by MoO2Cl2 Fernandes, Ana C.; Romão, Carlos C. Tetrahedron Letters, Vol. 48, Issue 52 https://doi.org/10.1016/j.tetlet.2007.10.106	journal	December 2007
CHEM21 selection guide of classical- and less classical-solvents Prat, Denis; Wells, Andy; Hayler, John Green Chemistry, Vol. 18, Issue 1 https://doi.org/10.1039/C5GC01008J	journal	January 2016
Nitrous Oxide as a Hydrogen Acceptor for the Dehydrogenative Coupling of Alcohols Gianetti, Thomas L.; Annen, Samuel P.; Santiso-Quinones, Gustavo Angewandte Chemie, Vol. 128, Issue 5 https://doi.org/10.1002/ange.201509288	journal	December 2015
Efficient synthesis of 2,5-dihydroxymethylfuran and 2,5-dimethylfuran from 5-hydroxymethylfurfural using mineral-derived Cu catalysts as versatile catalysts Zhu, Yifeng; Kong, Xiao; Zheng, Hongyan Catalysis Science & Technology, Vol. 5, Issue 8 https://doi.org/10.1039/C5CY00700C	journal	January 2015
Efficient carbon-supported heterogeneous molybdenum-dioxo catalyst for chemoselective reductive carbonyl coupling Liu, Shengsi; Li, Jiaqi; Jurca, Titel Catalysis Science & Technology, Vol. 7, Issue 11 https://doi.org/10.1039/C7CY00336F	journal	January 2017
Iron-Catalyzed Synthesis of Secondary Amines: On the Way to Green Reductive Aminations Stemmler, Tobias; Surkus, Annette-Enrika; Pohl, Marga-Martina ChemSusChem, Vol. 7, Issue 11 https://doi.org/10.1002/cssc.201402413	journal	September 2014
Nickel-Catalyzed Addition of Pyridine-N-oxides across Alkynes Kanyiva, Kyalo Stephen; Nakao, Yoshiaki; Hiyama, Tamejiro Angewandte Chemie International Edition, Vol. 46, Issue 46 https://doi.org/10.1002/anie.200703758	journal	November 2007
Reactions of Thiols with Sulfoxides. II. Kinetics and Mechanistic Implications Wallace, Thomas J.; Mahon, John J. Journal of the American Chemical Society, Vol. 86, Issue 19 https://doi.org/10.1021/ja01073a039	journal	October 1964
Reduction of sulfoxides catalyzed by oxo-complexes Cabrita, Ivânia; Sousa, Sara C. A.; Fernandes, Ana C. Tetrahedron Letters, Vol. 51, Issue 47 https://doi.org/10.1016/j.tetlet.2010.09.071	journal	November 2010
N -Bromosuccinimideand Iodine Catalyzed Highly Efficient Deoxygenation ofSulfoxides to Thioethers Using 3-Mercaptopropionic Acid under Mild ReactionConditions Karimi, Babak; Zareyee, Daryoush Synthesis, Issue 12 https://doi.org/10.1055/s-2003-40981	journal	January 2003
A Novel Method for the Deoxygenation of Sulfoxides with the PPh ₃ /Br ₂ /CuBr System Bahrami, Kiumars; Khodaei, Mohammad Mehdi; Khedri, Mohammad Chemistry Letters, Vol. 36, Issue 11 https://doi.org/10.1246/cl.2007.1324	journal	November 2007
A practical and chemoselective Mo-catalysed sulfoxide reduction protocol using a 3-mercaptopropyl-functionalized silica gel (MPS) García, Nuria; Fernández-Rodríguez, Manuel A.; García-García, Patricia RSC Advances, Vol. 6, Issue 32 https://doi.org/10.1039/C6RA03106D	journal	January 2016
Hydrogen activation by high-valent oxo-molybdenum(vi) and -rhenium(vii) and -(v) compounds Reis, Patrícia M.; Costa, Paulo Jorge; Romão, Carlos C. Dalton Transactions, Issue 13 https://doi.org/10.1039/b719375k	journal	January 2008
Chemoselective Hydrogenation of Nitro Compounds with Supported Gold Catalysts Corma, Avelino; Serna, Pedro Science, Vol. 313, Issue 5785, p. 332-334 https://doi.org/10.1126/science.1128383	journal	July 2006
A Facile and Efficient Iron-Catalyzed Reduction of Sulfoxides to Sulfides Enthaler, Stephan ChemCatChem, Vol. 3, Issue 4 https://doi.org/10.1002/cctc.201000400	journal	January 2011
Molybdenum-Catalyzed Deoxygenation of Heteroaromatic N- Oxides and Hydroxides using Pinacol as Reducing Agent Rubio-Presa, Rubén; Fernández-Rodríguez, Manuel A.; Pedrosa, María R. Advanced Synthesis & Catalysis, Vol. 359, Issue 10 https://doi.org/10.1002/adsc.201700071	journal	March 2017
Rhenium catalyzed sulfoxide reduction Arterburn, Jeffrey B.; Perry, Marc C. Tetrahedron Letters, Vol. 37, Issue 44 https://doi.org/10.1016/0040-4039(96)01836-9	journal	October 1996
Selective Deoxygenation of Sulfoxides to Sulfides with Phosphites Catalyzed by Dichlorodioxomolybdenum(VI) Sanz, Roberto; Escribano, Jaime; Aguado, Rafael Synthesis, Vol. 2004, Issue 10 https://doi.org/10.1055/s-2004-829104	journal	June 2004
Homogene und heterogene Katalyse – Brückenschlag durch Oberflächen-Organometallchemie Copéret, Christophe; Chabanas, Mathieu; Petroff Saint-Arroman, Romain Angewandte Chemie, Vol. 115, Issue 2 https://doi.org/10.1002/ange.200390040	journal	January 2003
Catalytic deoxygenation of pyridine N-oxides with N-fused porphyrin rhenium complexes Toganoh, Motoki; Fujino, Keitaro; Ikeda, Shinya Tetrahedron Letters, Vol. 49, Issue 9 https://doi.org/10.1016/j.tetlet.2007.12.117	journal	February 2008
Hydrogenation of Sulfoxides to Sulfides under Mild Conditions Using Ruthenium Nanoparticle Catalysts Mitsudome, Takato; Takahashi, Yusuke; Mizugaki, Tomoo Angewandte Chemie International Edition, Vol. 53, Issue 32 https://doi.org/10.1002/anie.201403425	journal	June 2014
Highly Efficient Gold Nanoparticle Catalyzed Deoxygenation of Amides, Sulfoxides, and Pyridine N-Oxides Mikami, Yusuke; Noujima, Akifumi; Mitsudome, Takato Chemistry - A European Journal, Vol. 17, Issue 6 https://doi.org/10.1002/chem.201003109	journal	January 2011
Homogeneous and Heterogeneous Catalysis: Bridging the Gap through Surface Organometallic Chemistry Copéret, Christophe; Chabanas, Mathieu; Petroff Saint-Arroman, Romain Angewandte Chemie International Edition, Vol. 42, Issue 2, p. 156-181 https://doi.org/10.1002/anie.200390072	journal	January 2003
Efficient Synthesis of Furfuryl Alcohol from H ₂ -Hydrogenation/Transfer Hydrogenation of Furfural Using Sulfonate Group Modified Cu Catalyst Gong, Wanbing; Chen, Chun; Zhang, Yong ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 3 https://doi.org/10.1021/acssuschemeng.6b02343	journal	February 2017
Mild and Efficient Deoxygenation of Sulfoxides to Sulfides Using HfCl ₄ /KBH ₄ System Zhang, Jianghua; Gao, Xinqin; Zhang, Chengyi Synthetic Communications, Vol. 40, Issue 12 https://doi.org/10.1080/00397910903161819	journal	May 2010
LiBH4(NaBH4)/Me3SiCl, ein ungewöhnlich starkes und vielseitig einsetzbares Reduktionsmittel Giannis, Athanassios; Sandhoff, Konrad Angewandte Chemie, Vol. 101, Issue 2 https://doi.org/10.1002/ange.19891010231	journal	February 1989
The deoxygenation of sulfoxide mediated by the Ph3P/Lewis acid combination and the application to the kinetic resolution of racemic phosphines using optically active sulfoxide Kikuchi, Satoshi; Konishi, Hiroyuki; Hashimoto, Yukihiko Tetrahedron, Vol. 61, Issue 14 https://doi.org/10.1016/j.tet.2005.01.127	journal	April 2005
Efficient catalytic greenhouse gas-free hydrogen and aldehyde formation from aqueous alcohol solutions Lohr, Tracy L.; Mouat, Aidan R.; Schweitzer, Neil M. Energy & Environmental Science, Vol. 10, Issue 7 https://doi.org/10.1039/C6EE03739A	journal	January 2017
Intramolecular catalysis of organic oxidation and reduction reactions: rapid and microscopically reversible thioether-sulfoxide interconversions in dilute acid Doi, Joyce Takahashi; Musker, W. Kenneth Journal of the American Chemical Society, Vol. 103, Issue 5 https://doi.org/10.1021/ja00395a027	journal	March 1981
Nickel-Catalyzed Addition of Pyridine-N-oxides across Alkynes Kanyiva, Kyalo Stephen; Nakao, Yoshiaki; Hiyama, Tamejiro Angewandte Chemie, Vol. 119, Issue 46 https://doi.org/10.1002/ange.200703758	journal	November 2007
Catalytic reduction of dimethyl sulfoxide and other sulfoxides with bromine - hydrobromic acid system. Aida, Tetsuo; Furukawa, Naomichi; Oae, Shigeru Tetrahedron Letters, Vol. 14, Issue 39 https://doi.org/10.1016/S0040-4039(01)87056-8	journal	January 1973
Methylrhenium trioxide as a catalyst for oxidations with molecular oxygen and for oxygen transfer Zhu, Zuolin; Espenson, James H. Journal of Molecular Catalysis A: Chemical, Vol. 103, Issue 2 https://doi.org/10.1016/1381-1169(95)00120-4	journal	October 1995
Hydrogenation of Sulfoxides to Sulfides under Mild Conditions Using Ruthenium Nanoparticle Catalysts Mitsudome, Takato; Takahashi, Yusuke; Mizugaki, Tomoo Angewandte Chemie, Vol. 126, Issue 32 https://doi.org/10.1002/ange.201403425	journal	June 2014
A survey of solvent selection guides Prat, Denis; Hayler, John; Wells, Andy Green Chem., Vol. 16, Issue 10 https://doi.org/10.1039/C4GC01149J	journal	January 2014
Reactivity of a Carbon-Supported Single-Site Molybdenum Dioxo Catalyst for Biodiesel Synthesis Mouat, Aidan R.; Lohr, Tracy L.; Wegener, Evan C. ACS Catalysis, Vol. 6, Issue 10 https://doi.org/10.1021/acscatal.6b01717	journal	September 2016
A novel method for the reduction of sulfoxides and pyridine N-oxides with the system silane/MoO2Cl2 Fernandes, Ana C.; Romão, Carlos C. Tetrahedron, Vol. 62, Issue 41 https://doi.org/10.1016/j.tet.2006.07.077	journal	October 2006
Dichlorodioxomolybdenum(VI) Complexes: Useful and Readily Available Catalysts in Organic Synthesis Hernández-Ruiz, Raquel; Sanz, Roberto Synthesis, Vol. 50, Issue 20 https://doi.org/10.1055/s-0037-1610236	journal	September 2018
Low‐Valent Molybdenum‐Based Dual Pre‐Catalysts for Highly Efficient Catalytic Epoxidation of Alkenes and Deoxygenation of Sulfoxides Krackl, Sebastian; Company, Anna; Enthaler, Stephan ChemCatChem, Vol. 3, Issue 7 https://doi.org/10.1002/cctc.201100007	journal	April 2011
Efficient deoxygenation methodologies catalyzed by oxo-molybdenum and oxo-rhenium complexes Sousa, Sara C. A.; Fernandes, Ana C. Coordination Chemistry Reviews, Vol. 284 https://doi.org/10.1016/j.ccr.2014.09.008	journal	February 2015
Efficient Synthesis of Furfuryl Alcohol and 2-Methylfuran from Furfural over Mineral-Derived Cu/ZnO Catalysts Yang, Xiaohai; Xiang, Xiaomin; Chen, Hongmei ChemCatChem, Vol. 9, Issue 15 https://doi.org/10.1002/cctc.201700279	journal	June 2017
Reduction of sulfoxides and pyridine-N-oxides over iron powder with water as hydrogen source promoted by carbon dioxide Ma, Ran; Liu, An-Hua; Huang, Cheng-Bin Green Chemistry, Vol. 15, Issue 5 https://doi.org/10.1039/c3gc40243f	journal	January 2013
An unprecedented use for glycerol: chemoselective reducing agent for sulfoxides García, Nuria; García-García, Patricia; Fernández-Rodríguez, Manuel A. Green Chemistry, Vol. 15, Issue 4 https://doi.org/10.1039/c3gc36908k	journal	January 2013
LiBH4(NaBH4)/Me3SiCl, an Unusually Strong and Versatile Reducing Agent Giannis, Athanassios; Sandhoff, Konrad Angewandte Chemie International Edition in English, Vol. 28, Issue 2 https://doi.org/10.1002/anie.198902181	journal	February 1989
Furfural: a renewable and versatile platform molecule for the synthesis of chemicals and fuels Mariscal, R.; Maireles-Torres, P.; Ojeda, M. Energy & Environmental Science, Vol. 9, Issue 4 https://doi.org/10.1039/C5EE02666K	journal	January 2016
Nitrous Oxide as a Hydrogen Acceptor for the Dehydrogenative Coupling of Alcohols Gianetti, Thomas L.; Annen, Samuel P.; Santiso-Quinones, Gustavo Angewandte Chemie International Edition, Vol. 55, Issue 5 https://doi.org/10.1002/anie.201509288	journal	December 2015
Highly Efficient Reduction of Sulfoxides with the System Borane/Oxo-rhenium Complexes ^† Fernandes, Ana C.; Fernandes, José A.; Romão, Carlos C. Organometallics, Vol. 29, Issue 21 https://doi.org/10.1021/om100450a	journal	November 2010
Chemoselective hydrogenation of nitroarenes and deoxygenation of pyridine N-oxides with H2 catalyzed by MoO2Cl2 Reis, Patrícia M.; Royo, Beatriz Tetrahedron Letters, Vol. 50, Issue 8 https://doi.org/10.1016/j.tetlet.2008.12.038	journal	February 2009
Biorefining: Heterogeneously Catalyzed Reactions of Carbohydrates for the Production of Furfural and Hydroxymethylfurfural Karinen, Reetta; Vilonen, Kati; Niemelä, Marita ChemSusChem, Vol. 4, Issue 8 https://doi.org/10.1002/cssc.201000375	journal	July 2011
Pyridine N -Oxide vs Pyridine Substrates for Rh(III)-Catalyzed Oxidative C–H Bond Functionalization Neufeldt, Sharon R.; Jiménez-Osés, Gonzalo; Huckins, John R. Journal of the American Chemical Society, Vol. 137, Issue 31 https://doi.org/10.1021/jacs.5b03535	journal	July 2015
Recent Advances in Catalytic Functionalization of N -Oxide Compounds via CH Bond Activation Yan, Guobing; Borah, Arun Jyoti; Yang, Minghua Advanced Synthesis & Catalysis, Vol. 356, Issue 11-12 https://doi.org/10.1002/adsc.201400203	journal	June 2014
A gentle and efficient route for the deoxygenation of sulfoxides using catecholborane (HBcat; cat=1,2-O2C6H4) Harrison, Daniel J.; Tam, Nga Chiu; Vogels, Christopher M. Tetrahedron Letters, Vol. 45, Issue 46 https://doi.org/10.1016/j.tetlet.2004.09.068	journal	November 2004
Deoxygenation of Sulfoxides to Sulfides with Thionyl Chloride and Triphenylphosphine: Competition with the Pummerer Reaction Jang, Yujin; Kim, Kyoung Tae; Jeon, Heung Bae The Journal of Organic Chemistry, Vol. 78, Issue 12 https://doi.org/10.1021/jo4008157	journal	June 2013

Similar Records

Efficient carbon-supported heterogeneous molybdenum-dioxo catalyst for chemoselective reductive carbonyl coupling

Journal Article · Mon May 08 00:00:00 EDT 2017 · Catalysis Science and Technology · OSTI ID:1512828

Liu, Shengsi; Li, Jiaqi; Jurca, Titel; +3 more

Aldehyde and Ketone Hydroboration Mediated by a Heterogeneous Single‐Site Molybdenum‐Dioxo Catalyst: Scope and Mechanistic Implications

Journal Article · Mon Jan 22 00:00:00 EST 2024 · ChemCatChem · OSTI ID:1512828

Liu, Yiqi; Agarwal, Amol; Ye, Liwei; +2 more

Reactivity of a Carbon-Supported Single-Site Molybdenum Dioxo Catalyst for Biodiesel Synthesis

Journal Article · Tue Aug 23 00:00:00 EDT 2016 · ACS Catalysis · OSTI ID:1512828

Mouat, Aidan R.; Lohr, Tracy L.; Wegener, Evan C.; +4 more

Title: Efficient Chemoselective Reduction of N ‐Oxides and Sulfoxides Using a Carbon‐Supported Molybdenum‐Dioxo Catalyst and Alcohol

Citation Formats

References (61)

Similar Records

Related Subjects