Copper-Catalyzed Oxidation of Hydrazones to Diazo Compounds Using Oxygen as the Terminal Oxidant

Liu, Wenbin; Twilton, Jack; Wei, Bo; Lee, Maizie; Hopkins, Melissa N.; Bacsa, John; Stahl, Shannon S.; Davies, Huw L.

doi:10.1021/acscatal.1c00264

Copper-Catalyzed Oxidation of Hydrazones to Diazo Compounds Using Oxygen as the Terminal Oxidant

Journal Article · Thu Feb 11 23:00:00 EST 2021 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.1c00264· OSTI ID:1779071

^[1]; ^[2]; Wei, Bo ^[3]; Lee, Maizie ^[3]; ^[2]; Bacsa, John ^[3]; ^[2]; ^[3]

Emory Univ., Atlanta, GA (United States); University of Wisconsin-Madison
Univ. of Wisconsin, Madison, WI (United States)
Emory Univ., Atlanta, GA (United States)

In this work, a mild method for accessing diazo compounds via aerobic oxidation of hydrazones is described. This catalytic transfor-mation employs a Cu(OAc)₂/pyridine catalyst and molecular oxygen from ambient air as the terminal oxidant, generating water as the sole byproduct and affording the desired diazo compounds within minutes at room temperature. A broad array of electronically diverse aryldiazo esters, ketones and amides can be accessed. Pyridine dramatically enhances the rate of the reaction by solubilizing the copper catalyst and serving as Brønsted base in the turnover-limiting proton-coupled oxidation of hydrazone by copper(II). Insights gained from mechanistic studies led to expansion of the scope of this method to include diaryl hydrazones, delivering diaryl diazomethane derivatives, which cannot be accessed via established diazo transfer meth-ods. The products of this method may be employed in rhodium carbene catalysis without isolation of the diazo intermediate to afford cyclopropane products in good yield with high enantioselectivity.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Wisconsin, Madison, WI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)

Grant/Contract Number:: FG02-05ER15690

OSTI ID:: 1779071

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 5 Vol. 11; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (63)

‘Bis(oxazolines)’ as Ligands for Self-Assembling Chiral Coordination Polymers— Structure of a Copper(I) Catalyst for the Enantioselective Cyclopropanation of Olefins Evans, David A.; Woerpel, Keith A.; Scott, Michael J. Angewandte Chemie International Edition in English, Vol. 31, Issue 4 https://doi.org/10.1002/anie.199204301	journal	April 1992
New Catalysts and Conditions for a CH Insertion Reaction Identified by High Throughput Catalyst Screening Burgess, Kevin; Lim, Hee-Jong; Porte, Alexander M. Angewandte Chemie International Edition in English, Vol. 35, Issue 2 https://doi.org/10.1002/anie.199602201	journal	February 1996
New Approaches to the Synthesis of Metal Carbenes Jia, Minqiang; Ma, Shengming Angewandte Chemie International Edition, Vol. 55, Issue 32 https://doi.org/10.1002/anie.201508119	journal	August 2016
Rapid Asymmetric Synthesis of Disubstituted Allenes by Coupling of Flow-Generated Diazo Compounds and Propargylated Amines Poh, Jian-Siang; Makai, Szabolcs; von Keutz, Timo Angewandte Chemie International Edition, Vol. 56, Issue 7 https://doi.org/10.1002/anie.201611067	journal	January 2017
An Immobilized-Dirhodium Hollow-Fiber Flow Reactor for Scalable and Sustainable C−H Functionalization in Continuous Flow Yoo, Chun-Jae; Rackl, Daniel; Liu, Wenbin Angewandte Chemie International Edition, Vol. 57, Issue 34 https://doi.org/10.1002/anie.201805528	journal	July 2018
Catalytic Desymmetric Cycloaddition of Diaziridines with Metalloenolcarbenes: The Role of Donor–Acceptor Cyclopropenes Zheng, Haifeng; Doyle, Michael P. Angewandte Chemie International Edition, Vol. 58, Issue 36 https://doi.org/10.1002/anie.201906754	journal	September 2019
Rhodium‐Catalyzed Enantioselective [4+2] Cycloadditions of Vinylcarbenes with Dienes Zhang, Bowen; Davies, Huw M. L. Angewandte Chemie International Edition, Vol. 59, Issue 12 https://doi.org/10.1002/anie.201914354	journal	February 2020
Transition Metal Catalyzed Insertion Reactions with Donor/Donor Carbenes Bergstrom, Benjamin D.; Nickerson, Leslie A.; Shaw, Jared T. Angewandte Chemie International Edition, Vol. 60, Issue 13 https://doi.org/10.1002/anie.202007001	journal	October 2020
Versuche zur Herstellung isomerer Diazoverbindungen bezw. Hydrazone Staudinger, H.; Gaule, Alice Berichte der deutschen chemischen Gesellschaft, Vol. 49, Issue 2 https://doi.org/10.1002/cber.19160490251	journal	July 1916
Facile One-Pot Synthesis of [1, 2, 3]Triazolo[1, 5- a ]Pyridines from 2-Acylpyridines by Copper(II)-Catalyzed Oxidative NN Bond Formation Hirayama, Tasuku; Ueda, Satoshi; Okada, Takahiro Chemistry - A European Journal, Vol. 20, Issue 14 https://doi.org/10.1002/chem.201302997	journal	February 2014
Potassium N -Iodo p -Toluenesulfonamide (TsNIK, Iodamine-T): A New Reagent for the Oxidation of Hydrazones to Diazo Compounds Nicolle, Simon M.; Moody, Christopher J. Chemistry - A European Journal, Vol. 20, Issue 15 https://doi.org/10.1002/chem.201304656	journal	March 2014
Taming Hazardous Chemistry in Flow: The Continuous Processing of Diazo and Diazonium Compounds Deadman, Benjamin J.; Collins, Stuart G.; Maguire, Anita R. Chemistry - A European Journal, Vol. 21, Issue 6 https://doi.org/10.1002/chem.201404348	journal	November 2014
The Generation of Diazo Compounds in Continuous-Flow Hock, Katharina J.; Koenigs, Rene M. Chemistry - A European Journal, Vol. 24, Issue 42 https://doi.org/10.1002/chem.201800136	journal	June 2018
Silver‐Catalyzed Asymmetric Insertion into Phenolic O−H Bonds using Aryl Diazoacetates and Theoretical Mechanistic Studies Harada, Shingo; Tanikawa, Koki; Homma, Haruka Chemistry – A European Journal, Vol. 25, Issue 52 https://doi.org/10.1002/chem.201902126	journal	July 2019
The Use of Tosylhydrazone Salts as a Safe Alternative for Handling Diazo Compounds and Their Applications in Organic Synthesis Fulton, J. Robin; Aggarwal, Varinder K.; de Vicente, Javier European Journal of Organic Chemistry, Vol. 2005, Issue 8 https://doi.org/10.1002/ejoc.200400700	journal	April 2005
Formation of diazoketones and azines by improved oxidation of ketohydrazones using Cu(acac)2 as a catalyst Ibata, Toshikazu; Singh, Girija S. Tetrahedron Letters, Vol. 35, Issue 16 https://doi.org/10.1016/S0040-4039(00)77176-0	journal	April 1994
Organic synthesis by means of metal, complexes. Tsuji, Jiro; Takahashi, Hidetaka; Kajimoto, Tsunesuke Tetrahedron Letters, Vol. 14, Issue 46 https://doi.org/10.1016/S0040-4039(01)87279-8	journal	January 1973
Facile synthesis of 9-azajulolidine and its application to post-Ullmann reactions Wong, Ken-Tsung; Ku, Sung-Yu; Yen, Feng-Wen Tetrahedron Letters, Vol. 48, Issue 29 https://doi.org/10.1016/j.tetlet.2007.05.094	journal	July 2007
Synthesis and esterification reactions of aryl diazomethanes derived from hydrazone oxidations catalyzed by TEMPO Perusquía-Hernández, Carolina; Lara-Issasi, Gonzalo R.; Frontana-Uribe, Bernardo A. Tetrahedron Letters, Vol. 54, Issue 25 https://doi.org/10.1016/j.tetlet.2013.04.079	journal	June 2013
Synthesis and evaluation of 1,1,7,7-tetramethyl-9-azajulolidine (TMAJ) as a highly active derivative of N,N-dimethylaminopyridine Tsutsumi, Tomohiro; Saitoh, Arisa; Kasai, Tomoyo Tetrahedron Letters, Vol. 61, Issue 26 https://doi.org/10.1016/j.tetlet.2020.152047	journal	June 2020
Modern Organic Synthesis with α-Diazocarbonyl Compounds Ford, Alan; Miel, Hugues; Ring, Aoife Chemical Reviews, Vol. 115, Issue 18 https://doi.org/10.1021/acs.chemrev.5b00121	journal	August 2015
Transition-Metal-Catalyzed Cross-Couplings through Carbene Migratory Insertion Xia, Ying; Qiu, Di; Wang, Jianbo Chemical Reviews, Vol. 117, Issue 23 https://doi.org/10.1021/acs.chemrev.7b00382	journal	June 2017
Copper-Catalyzed Carbenoid Insertion Reactions of α-Diazoesters and α-Diazoketones into Si–H and S–H Bonds Keipour, Hoda; Jalba, Angela; Delage-Laurin, Léo The Journal of Organic Chemistry, Vol. 82, Issue 6 https://doi.org/10.1021/acs.joc.6b02998	journal	March 2017
Finding Opportunities from Surprises and Failures. Development of Rhodium-Stabilized Donor/Acceptor Carbenes and Their Application to Catalyst-Controlled C–H Functionalization Davies, Huw M. L. The Journal of Organic Chemistry, Vol. 84, Issue 20 https://doi.org/10.1021/acs.joc.9b02428	journal	August 2019
The First Kilogram Synthesis of Beclabuvir, an HCV NS5B Polymerase Inhibitor Bien, Jeffrey; Davulcu, Akin; DelMonte, Albert J. Organic Process Research & Development, Vol. 22, Issue 10 https://doi.org/10.1021/acs.oprd.8b00214	journal	August 2018
Thermal Stability and Explosive Hazard Assessment of Diazo Compounds and Diazo Transfer Reagents Green, Sebastian P.; Wheelhouse, Katherine M.; Payne, Andrew D. Organic Process Research & Development, Vol. 24, Issue 1 https://doi.org/10.1021/acs.oprd.9b00422	journal	November 2019
Metal-Free C–H Functionalization of Alkanes by Aryldiazoacetates Tortoreto, Cecilia; Rackl, Daniel; Davies, Huw M. L. Organic Letters, Vol. 19, Issue 4 https://doi.org/10.1021/acs.orglett.6b03681	journal	February 2017
Copper-Catalyzed, Stereoselective Cross-Coupling of Cyclic Allyl Boronic Acids with α-Diazoketones Wang, Dong; Szabó, Kálmán J. Organic Letters, Vol. 19, Issue 7 https://doi.org/10.1021/acs.orglett.7b00433	journal	March 2017
Rhodium-Stabilized Diarylcarbenes Behaving as Donor/Acceptor Carbenes Lee, Maizie; Ren, Zhi; Musaev, Djamaladdin G. ACS Catalysis, Vol. 10, Issue 11 https://doi.org/10.1021/acscatal.0c01131	journal	April 2020
Overcoming Scope Limitations in Cross-Coupling of Diazo Nucleophiles by Manipulating Catalyst Speciation and Using Flow Diazo Generation Sullivan, Ryan J.; Freure, Garrett P. R.; Newman, Stephen G. ACS Catalysis, Vol. 9, Issue 6 https://doi.org/10.1021/acscatal.9b01180	journal	May 2019
In Situ Kinetic Studies of Rh(II)-Catalyzed Asymmetric Cyclopropanation with Low Catalyst Loadings Wei, Bo; Sharland, Jack C.; Lin, Patricia ACS Catalysis, Vol. 10, Issue 2 https://doi.org/10.1021/acscatal.9b04595	journal	December 2019
Copper(I) catalysis in cyclopropanations with diazo compounds. Role of olefin coordination Salomon, Robert G.; Kochi, Jay K. Journal of the American Chemical Society, Vol. 95, Issue 10 https://doi.org/10.1021/ja00791a038	journal	May 1973
Mechanism of the Wolff rearrangement Csizmadia, Imre G.; Font, J.; Strausz, Otto P. Journal of the American Chemical Society, Vol. 90, Issue 26 https://doi.org/10.1021/ja01028a041	journal	December 1968
o -Iodoxybenzoic Acid (IBX) as a Viable Reagent in the Manipulation of Nitrogen- and Sulfur-Containing Substrates: Scope, Generality, and Mechanism of IBX-Mediated Amine Oxidations and Dithiane Deprotections Nicolaou, K. C.; Mathison, Casey J. N.; Montagnon, Tamsyn Journal of the American Chemical Society, Vol. 126, Issue 16 https://doi.org/10.1021/ja0400382	journal	April 2004
Enantioselective Si–H Insertion Reactions of Diarylcarbenes for the Synthesis of Silicon-Stereogenic Silanes Jagannathan, Jake R.; Fettinger, James C.; Shaw, Jared T. Journal of the American Chemical Society, Vol. 142, Issue 27 https://doi.org/10.1021/jacs.0c04533	journal	June 2020
Enantioselective Diarylcarbene Insertion into Si–H Bonds Induced by Electronic Properties of the Carbenes Yang, Liang-Liang; Evans, Declan; Xu, Bin Journal of the American Chemical Society, Vol. 142, Issue 28 https://doi.org/10.1021/jacs.0c04725	journal	June 2020
Asymmetric Catalysis with Organic Azides and Diazo Compounds Initiated by Photoinduced Electron Transfer Huang, Xiaoqiang; Webster, Richard D.; Harms, Klaus Journal of the American Chemical Society, Vol. 138, Issue 38 https://doi.org/10.1021/jacs.6b07692	journal	September 2016
Advantageous Syntheses of Diazo Compounds by Oxidation of Hydrazones with Lead Tetraacetate in Basic Environments Holton, Terrence L.; Schechter, Harold The Journal of Organic Chemistry, Vol. 60, Issue 15 https://doi.org/10.1021/jo00120a013	journal	July 1995
Communications- Preparation of α-Diazo Ketones Morrison, Harry; Danishefsky, Samuel; Yates, Peter The Journal of Organic Chemistry, Vol. 26, Issue 7 https://doi.org/10.1021/jo01351a658	journal	July 1961
The use of Silver Oxide in the Preparation of Diaryldiazomethanes Schroeder, William; Katz, Leon The Journal of Organic Chemistry, Vol. 19, Issue 5 https://doi.org/10.1021/jo01370a003	journal	May 1954
Effective and Highly Stereoselective Coupling with Vinyldiazomethanes To Form Symmetrical Trienes Doyle, Michael P.; Yan, Ming The Journal of Organic Chemistry, Vol. 67, Issue 2 https://doi.org/10.1021/jo016135k	journal	January 2002
Diazo Preparation via Dehydrogenation of Hydrazones with “Activated” DMSO Javed, Muhammad I.; Brewer, Matthias Organic Letters, Vol. 9, Issue 9 https://doi.org/10.1021/ol070515w	journal	April 2007
Enantioselective Synthesis of Trifluoromethyl-Substituted Cyclopropanes Denton, Justin R.; Sukumaran, Dinesh; Davies, Huw M. L. Organic Letters, Vol. 9, Issue 14 https://doi.org/10.1021/ol070714f	journal	July 2007
Thermally Induced Cycloadditions of Donor/Acceptor Carbenes Ovalles, Stephanie R.; Hansen, Jørn H.; Davies, Huw M. L. Organic Letters, Vol. 13, Issue 16 https://doi.org/10.1021/ol201628d	journal	August 2011
Diversity-Oriented Approach to CF ₃ CHF-, CF ₃ CFBr-, CF ₃ CF ₂ -, (CF ₃ ) ₂ CH-, and CF ₃ (SCF ₃ )CH-Substituted Arenes from 1-(Diazo-2,2,2-trifluoroethyl)arenes Emer, Enrico; Twilton, Jack; Tredwell, Matthew Organic Letters, Vol. 16, Issue 22 https://doi.org/10.1021/ol5030184	journal	November 2014
Iodine-catalyzed diazo activation to access radical reactivity Li, Pan; Zhao, Jingjing; Shi, Lijun Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04331-4	journal	May 2018
Dirhodium tetracarboxylates as catalysts for selective intermolecular C–H functionalization Davies, Huw M. L.; Liao, Kuangbiao Nature Reviews Chemistry, Vol. 3, Issue 6 https://doi.org/10.1038/s41570-019-0099-x	journal	May 2019
Flow chemistry as a discovery tool to access sp ² –sp ³ cross-coupling reactions via diazo compounds Tran, Duc N.; Battilocchio, Claudio; Lou, Shing-Bong Chemical Science, Vol. 6, Issue 2 https://doi.org/10.1039/C4SC03072A	journal	January 2015
Dinitrogen extrusion from enoldiazo compounds under thermal conditions: synthesis of donor–acceptor cyclopropenes Deng, Yongming; Jing, Changcheng; Doyle, Michael P. Chemical Communications, Vol. 51, Issue 65 https://doi.org/10.1039/C5CC05006E	journal	January 2015
Taming hazardous chemistry by continuous flow technology Movsisyan, M.; Delbeke, E. I. P.; Berton, J. K. E. T. Chemical Society Reviews, Vol. 45, Issue 18 https://doi.org/10.1039/C5CS00902B	journal	January 2016
Thermally induced N–S bond insertion reaction of diazo compounds with N -sulfenylsuccinimides: synthesis of sulfides and mechanism studies Zhang, Xiaolu; Zheng, Yang; Qiu, Lihua Organic & Biomolecular Chemistry, Vol. 16, Issue 1 https://doi.org/10.1039/C7OB02488F	journal	January 2018
Recent developments in photochemical reactions of diazo compounds Ciszewski, Łukasz W.; Rybicka-Jasińska, Katarzyna; Gryko, Dorota Organic & Biomolecular Chemistry, Vol. 17, Issue 3 https://doi.org/10.1039/C8OB02703J	journal	January 2019
Blue light-promoted photolysis of aryldiazoacetates Jurberg, Igor D.; Davies, Huw M. L. Chemical Science, Vol. 9, Issue 22 https://doi.org/10.1039/C8SC01165F	journal	January 2018
Recent progress on donor and donor–donor carbenes Zhu, Dong; Chen, Lianfen; Fan, Hanlin Chemical Society Reviews, Vol. 49, Issue 3 https://doi.org/10.1039/C9CS00542K	journal	January 2020
Fe ^II -catalysed insertion reaction of α-diazocarbonyls into X–H bonds (X = Si, S, N, and O) in dimethyl carbonate as a suitable solvent alternative Tanbouza, Nour; Keipour, Hoda; Ollevier, Thierry RSC Advances, Vol. 9, Issue 54 https://doi.org/10.1039/C9RA07203A	journal	January 2019
Oxidation with nickel peroxide. The preparation of diazo-compounds from hydrazones Nakagawa, Kunio; Onoue, Hiroshi; Minami, Ky?tji Chemical Communications (London), Issue 20 https://doi.org/10.1039/c19660000730	journal	January 1966
Catalytic X–H insertion reactions based on carbenoids Gillingham, Dennis; Fei, Na Chemical Society Reviews, Vol. 42, Issue 12 https://doi.org/10.1039/c3cs35496b	journal	January 2013
The preparation of secondary aliphatic diazo-compounds from hydrazones Day, A. C.; Raymond, P.; Southam, R. M. Journal of the Chemical Society C: Organic https://doi.org/10.1039/j39660000467	journal	January 1966
924. The decomposition of toluene-p-sulphonylhydrazones by alkali Bamford, W. R.; Stevens, T. S. Journal of the Chemical Society (Resumed) https://doi.org/10.1039/jr9520004735	journal	January 1952
Diazotransfer Reactions with p -Acetamidobenzenesulfonyl Azide Baum, Jonathan S.; Shook, David A.; Davies, Huw M. L. Synthetic Communications, Vol. 17, Issue 14 https://doi.org/10.1080/00397918708063988	journal	October 1987
Structural comparison between dimeric copper(II) formate and acetate in pyridine and urea adducts Uekusa, H.; Ohba, S.; Saito, Y. Acta Crystallographica Section C Crystal Structure Communications, Vol. 45, Issue 3 https://doi.org/10.1107/S0108270188011904	journal	March 1989
A Convenient Synthesis of Diazo Compounds by Catalytic Dehydrogenation of Hydrazones with Cobalt Schiff base Complex-Oxygen System Nishinaga, Akira; Yamazaki, Shigekazu; Matsuura, Teruo Chemistry Letters, Vol. 15, Issue 4 https://doi.org/10.1246/cl.1986.505	journal	April 1986
Aerial Oxidation of Some 2-Pyridyl Ketone Hydrazones Catalyzed by Cu2+. Physical Properties of Reaction Products. Mori, Hisakazu; Sakamoto, Kaori; Mashito, Sachie Chemical and Pharmaceutical Bulletin, Vol. 41, Issue 11 https://doi.org/10.1248/cpb.41.1944	journal	January 1993

Similar Records

Heterogeneous Fe-N-C Catalyst for Aerobic Dehydrogenation of Hydrazones to Diazo Compounds Used for Carbene Transfer

Journal Article · Wed May 08 00:00:00 EDT 2024 · Journal of the American Chemical Society · OSTI ID:2429384

Diazo compounds: properties and synthesis

Book · Tue Dec 31 23:00:00 EST 1985 · OSTI ID:6035283

Bis(oxazoline)-copper complexes as catalysts for the enantioselective cyclopropanation of olefins

Thesis/Dissertation · Tue Dec 31 23:00:00 EST 1991 · OSTI ID:5719851

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
aerobic oxidation
copper
dehydrogenation
diazo compounds
hydrazones
mechanism

Copper-Catalyzed Oxidation of Hydrazones to Diazo Compounds Using Oxygen as the Terminal Oxidant

Citation Formats

References (63)

Similar Records

Related Subjects