Cu(II)-Catalyzed H/D exchange of indole derivatives

Bai, Jing-Wen; Guo, Lei; Chen, Meng-Zhe; Advincula, Rigoberto; Zhang, Hong-Hai

doi:10.1016/j.tetlet.2023.154884

Title: Cu(II)-Catalyzed H/D exchange of indole derivatives

Journal Article · 08 December 2023 · Tetrahedron Letters

DOI: https://doi.org/10.1016/j.tetlet.2023.154884 · OSTI ID:2301633

Bai, Jing-Wen ^[1]; Guo, Lei ^[1]; Chen, Meng-Zhe ^[2]; Advincula, Rigoberto ^[3]; Zhang, Hong-Hai ^[3]

Nanjing Tech Univ. (China)
National Tsing Hua Univ., Hsinchu (Taiwan)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)

Cu(OTf)₂ was explored as an efficient catalyst for hydrogen deuterium (H/D) exchange of indole derivatives. The advantage of this reaction is that deuteration selectivity can be adjusted by changing reaction parameters. When the reaction was performed with 10 mol% of Cu(OTf)₂ as a catalyst in dioxane at 80 °C, deuteration preferentially occurred at C3 position of indole with high atom% deuterium incorporation. Furthermore, per-deuterated indole derivatives could be achieved by performing the reaction with higher catalyst loading in toluene at 120 °C. In conclusion, performing the reaction on a continuous flow reactor facilitates the scale-up process, affording deuterated products with a throughput of 3.9 g/h.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2301633

Journal Information:: Tetrahedron Letters, Journal Name: Tetrahedron Letters Journal Issue: 1 Vol. 135; ISSN 0040-4039

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (37)

Afterglow Organic Light-Emitting Diode Kabe, Ryota; Notsuka, Naoto; Yoshida, Kou Advanced Materials, Vol. 28, Issue 4 https://doi.org/10.1002/adma.201504321	journal	November 2015
The Renaissance of H/D Exchange Atzrodt, Jens; Derdau, Volker; Fey, Thorsten Angewandte Chemie International Edition, Vol. 46, Issue 41 https://doi.org/10.1002/anie.200700039	journal	October 2007
Cryptocatalytic 1,2-Alkene Migration in a σ-Alkyl Palladium Diene Complex Evans, Louise A.; Fey, Natalie; Lloyd-Jones, Guy C. Angewandte Chemie International Edition, Vol. 48, Issue 34 https://doi.org/10.1002/anie.200901468	journal	July 2009
On the Interpretation of Deuterium Kinetic Isotope Effects in CH Bond Functionalizations by Transition-Metal Complexes Simmons, Eric M.; Hartwig, John F. Angewandte Chemie International Edition, Vol. 51, Issue 13 https://doi.org/10.1002/anie.201107334	journal	March 2012
Regioselective and Stereospecific Deuteration of Bioactive Aza Compounds by the Use of Ruthenium Nanoparticles Pieters, Grégory; Taglang, Céline; Bonnefille, Eric Angewandte Chemie International Edition, Vol. 53, Issue 1 https://doi.org/10.1002/anie.201307930	journal	November 2013
C−H Functionalisation for Hydrogen Isotope Exchange Atzrodt, Jens; Derdau, Volker; Kerr, William J. Angewandte Chemie International Edition, Vol. 57, Issue 12 https://doi.org/10.1002/anie.201708903	journal	February 2018
Multiple Site Hydrogen Isotope Labelling of Pharmaceuticals Daniel‐Bertrand, Marion; Garcia‐Argote, Sébastien; Palazzolo, Alberto Angewandte Chemie International Edition, Vol. 59, Issue 47 https://doi.org/10.1002/anie.202008519	journal	September 2020
Kinetic Isotope Effects in Asymmetric Reactions Giagou, Thomas; Meyer, Matthew P. Chemistry - A European Journal, Vol. 16, Issue 35 https://doi.org/10.1002/chem.201001018	journal	July 2010
Stereochemistry and Mechanism of the Brønsted Acid Catalyzed Intramolecular Hydrofunctionalization of an Unactivated Cyclic Alkene McKinney Brooner, Rachel E.; Widenhoefer, Ross A. Chemistry – A European Journal, Vol. 17, Issue 22 https://doi.org/10.1002/chem.201003128	journal	April 2011
Metal-catalysed hydrogen isotope exchange labelling: a brief overview Lockley, William J. S.; Heys, J. Richard Journal of Labelled Compounds and Radiopharmaceuticals, Vol. 53, Issue 11-12 https://doi.org/10.1002/jlcr.1851	journal	September 2010
Isotope chemistry; a useful tool in the drug discovery arsenal Elmore, Charles S.; Bragg, Ryan A. Bioorganic & Medicinal Chemistry Letters, Vol. 25, Issue 2 https://doi.org/10.1016/j.bmcl.2014.11.051	journal	January 2015
General method of obtaining deuterium-labeled heterocyclic compounds using neutral D₂O with heterogeneous Pd/C Esaki, Hiroyoshi; Ito, Nobuhiro; Sakai, Shino Tetrahedron, Vol. 62, Issue 47, p. 10954-10961 https://doi.org/10.1016/j.tet.2006.08.088	journal	November 2006
A practical and efficient method for late-stage deuteration of terminal alkynes with silver salt as catalyst Wu, Ding-Chuan; Bai, Jing-Wen; Guo, Lei Tetrahedron Letters, Vol. 66 https://doi.org/10.1016/j.tetlet.2020.152807	journal	March 2021
Natural Eumelanin and Its Derivatives as Multifunctional Materials for Bioinspired Applications: A Review Xie, Wanjie; Pakdel, Esfandiar; Liang, Yujia Biomacromolecules, Vol. 20, Issue 12 https://doi.org/10.1021/acs.biomac.9b01413	journal	November 2019
Azacyclo-indoles and Phenolics from the Flowers of Juglans regia Li, Qian; Deng, An-Jun; Li, Li Journal of Natural Products, Vol. 80, Issue 8 https://doi.org/10.1021/acs.jnatprod.6b00887	journal	July 2017
Mushroom-Derived Indole Alkaloids Homer, Joshua A.; Sperry, Jonathan Journal of Natural Products, Vol. 80, Issue 7 https://doi.org/10.1021/acs.jnatprod.7b00390	journal	June 2017
Deuteration and Polymers: Rich History with Great Potential Li, Lengwan; Jakowski, Jacek; Do, Changwoo Macromolecules, Vol. 54, Issue 8 https://doi.org/10.1021/acs.macromol.0c02284	journal	March 2021
A Perspective on Continuous Flow Chemistry in the Pharmaceutical Industry Baumann, Marcus; Moody, Thomas S.; Smyth, Megan Organic Process Research & Development, Vol. 24, Issue 10 https://doi.org/10.1021/acs.oprd.9b00524	journal	January 2020
Catalytic Deuteration of C(sp ² )–H Bonds of Substituted (Hetero)arenes in a Pt(II) CNN-Pincer Complex/2,2,2-Trifluoroethanol- d ₁ System: Effect of Substituents on the Reaction Rate and Selectivity Kramer, Morgan; Watts, David; Vedernikov, Andrei N. Organometallics, Vol. 39, Issue 22 https://doi.org/10.1021/acs.organomet.0c00652	journal	November 2020
Synthesis of Multideuterated (Hetero)aryl Bromides by Ag(I)-Catalyzed H/D Exchange Hu, Guang-Qi; Bai, Jing-Wen; Li, En-Ci Organic Letters, Vol. 23, Issue 5 https://doi.org/10.1021/acs.orglett.0c04139	journal	February 2021
Ag ₂ CO ₃ -Catalyzed H/D Exchange of Five-Membered Heteroarenes at Ambient Temperature Li, En-Ci; Hu, Guang-Qi; Zhu, Yu-Xing Organic Letters, Vol. 21, Issue 17 https://doi.org/10.1021/acs.orglett.9b02369	journal	August 2019
Versatile Regioselective Deuteration of Indoles via Transition-Metal-Catalyzed H/D Exchange Zhang, Jinquan; Zhang, Shuaizhong; Gogula, Thirupathi ACS Catalysis, Vol. 10, Issue 14 https://doi.org/10.1021/acscatal.0c01674	journal	June 2020
Site-Selective Silver-Catalyzed C–H Bond Deuteration of Five-Membered Aromatic Heterocycles and Pharmaceuticals Tlahuext-Aca, Adrian; Hartwig, John F. ACS Catalysis, Vol. 11, Issue 3 https://doi.org/10.1021/acscatal.0c04917	journal	January 2021
Site-Selective Deuteration of N-Heterocycles via Iridium-Catalyzed Hydrogen Isotope Exchange Kerr, William J.; Lindsay, David M.; Owens, Philippa K. ACS Catalysis, Vol. 7, Issue 10 https://doi.org/10.1021/acscatal.7b02682	journal	September 2017
Synthetic Approaches to 3-(2-Nitroalkyl) Indoles and Their Use to Access Tryptamines and Related Bioactive Compounds Lancianesi, Stefano; Palmieri, Alessandro; Petrini, Marino Chemical Reviews, Vol. 114, Issue 14 https://doi.org/10.1021/cr400676v	journal	June 2014
Lipidomics Reveals Dramatic Physiological Kinetic Isotope Effects during the Enzymatic Oxygenation of Polyunsaturated Fatty Acids Ex Vivo Navratil, Aaron R.; Shchepinov, Mikhail S.; Dennis, Edward A. Journal of the American Chemical Society, Vol. 140, Issue 1 https://doi.org/10.1021/jacs.7b09493	journal	December 2017
Ni(I)–X Complexes Bearing a Bulky α-Diimine Ligand: Synthesis, Structure, and Superior Catalytic Performance in the Hydrogen Isotope Exchange in Pharmaceuticals Zarate, Cayetana; Yang, Haifeng; Bezdek, Máté J. Journal of the American Chemical Society, Vol. 141, Issue 12 https://doi.org/10.1021/jacs.9b00939	journal	March 2019
Using Deuterium in Drug Discovery: Leaving the Label in the Drug Gant, Thomas G. Journal of Medicinal Chemistry, Vol. 57, Issue 9 https://doi.org/10.1021/jm4007998	journal	December 2013
Selective Ru(0)-Catalyzed Deuteration of Electron-Rich and Electron-Poor Nitrogen-Containing Heterocycles Gröll, Birgit; Schnürch, Michael; Mihovilovic, Marko D. The Journal of Organic Chemistry, Vol. 77, Issue 9 https://doi.org/10.1021/jo300219v	journal	April 2012
The isotopic effects of deuteration on optoelectronic properties of conducting polymers Shao, Ming; Keum, Jong; Chen, Jihua Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4180	journal	January 2014
Isotope effect in spin response of π-conjugated polymer films and devices Nguyen, Tho D.; Hukic-Markosian, Golda; Wang, Fujian Nature Materials, Vol. 9, Issue 4 https://doi.org/10.1038/nmat2633	journal	February 2010
Geometric isotope effect of deuteration in a hydrogen-bonded host–guest crystal Shi, Chao; Zhang, Xi; Yu, Chun-Hua Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-02931-8	journal	February 2018
Spatially confined protein assembly in hierarchical mesoporous metal-organic framework Wang, Xiaoliang; He, Lilin; Sumner, Jacob Nature Communications, Vol. 14, Issue 1 https://doi.org/10.1038/s41467-023-36533-w	journal	February 2023
Ag( i )-Mediated hydrogen isotope exchange of mono-fluorinated (hetero)arenes Hu, Guang-Qi; Li, En-Ci; Zhang, Hong-Hai Organic & Biomolecular Chemistry, Vol. 18, Issue 34 https://doi.org/10.1039/D0OB01273D	journal	January 2020
Silver-catalyzed regioselective deuteration of (hetero)arenes and α-deuteration of 2-alkyl azaarenes Dong, Baobiao; Cong, Xuefeng; Hao, Na RSC Advances, Vol. 10, Issue 43 https://doi.org/10.1039/D0RA02358B	journal	January 2020
Silver salt enabled H/D exchange at the β-position of thiophene rings: synthesis of fully deuterated thiophene derivatives Sheng, Fei-Fei; Li, En-Ci; Bai, Jing-Wen Organic & Biomolecular Chemistry, Vol. 20, Issue 6 https://doi.org/10.1039/D1OB02285G	journal	January 2022
C-H Bond Activation by Water on a Palladium or Platinum Metal Surface Matsubara, Seijiro; Asano, Keisuke; Kajita, Yuichi Synthesis, Vol. 2007, Issue 13 https://doi.org/10.1055/s-2007-983738	journal	July 2007

Similar Records

Syntheses and reactivities of indole and indolyl complexes of (cymene)ruthenium(II)

Journal Article · 1995 · Organometallics · OSTI ID:28696

Chen, S; Carperos, V; Noll, B; +2 more

Catalytic dehydration of biomass derived 1-propanol to propene over M-ZSM-5 (M = H, V, Cu, or Zn)

Journal Article · 2017 · Industrial and Engineering Chemistry Research · OSTI ID:1350920

Lepore, Andrew W.; Li, Zhenglong; Davison, Brian H.; +3 more

Using indole to inhibit copper corrosion in aerated 0.5 M sulfuric acid

Journal Article · 1998 · Corrosion · OSTI ID:644355

Quartarone, G; Moretti, G; Bellomi, T; +2 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Cu(II)-Catalyzed H/D exchange of indole derivatives

Citation Formats

References (37)

Similar Records

Related Subjects