Journal of the American Chemical Society
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(13) Zhang, Z. –H.; Dong, X.–Y.; Du, X.–Y.; Gu, Q.–S.; Li, Z.‐L.;
AUTHOR INFORMATION
Corresponding Author
Liu, X.–Y. Copper‐Catalyzed Enantioselective So‐
nogashira–Type Oxidative Cross‐Coupling of Unactivated
C(sp3)−H Bonds with Alkynes. Nat. Commun. 2019, 10,
5689.
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* T.H. Warren − Department of Chemistry, Georgetown
University, Box 571227−1227, Washington, D.C. 20057, United
States.
(14) Zhang, G.; Yi, H.; Zhang, G.; Deng, Y.; Bai, R.; Zhang, H.;
Miller, J. T.; Kropf, A. J.; Bunel, E. E.; Lei, A. Direct Ob‐
servation of Reduction of Cu(II) to Cu(I) by Terminal Al‐
kynes. J. Am. Chem. Soc. 2014, 136, 924–926.
Email: thw@georgetown.edu
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(15) Bai, R.; Zhang, G.; Yi, H.; Huang, Z.; Qi, X.; Liu, C.; Miller,
J. T.; Kropf, A. J.; Bunel, E. E.; Lan, Y.; Lei, A. Cu(II)–Cu(I)
Synergistic Cooperation to Lead the Alkyne C–H Activa‐
tion. J. Am. Chem. Soc. 2014, 136, 16760–16763.
ORCID
Timothy H. Warren: 0000‐0001‐9217‐8890.
Abolghasem Bakhoda: 0000‐0002‐3222‐8873.
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(16) Feng, L.; Hu, T.; Zhang, S.; Xiong, H–Y.; Zhang, G. Cop‐
per–Mediated Deacylative Coupling of Ynones via C–C
Bond Activation under Mild Conditions. Org. Lett. 2019,
21, 9487–9492.
(17) Hamada, T.; Ye, X.; Stahl, S. S. Copper–Catalyzed Aerobic
Oxidative Amidation of Terminal Alkynes: Efficient Syn‐
thesis of Ynamides. J. Am. Chem. Soc. 2008, 130, 833–835.
(18) Wang, L.; Huang, H.; Priebbenow, D. L.; Pan, F.–F.; Bolm,
C. Copper–Catalyzed Oxidative Cross‐Coupling of Sul‐
foximines and Alkynes. Angew. Chem. Int. Ed. 2013, 52,
3478–3480.
(19) Fu, L.; Zhang, Z.; Chen, P.; Lin,Z.; Liu, G. Enantioselective
Copper-Catalyzed Alkynylation of Benzylic C-H Bonds via
Radical Relay. J. Am. Chem. Soc. 2020, 142, 12493‐12500.
(20) Hazra, A.; Lee, T. M.; Chiu, J. F.; Lalic, G. Photoinduced
Copper–Catalyzed Coupling of Terminal Alkynes and Al‐
kyl Iodides. Angew. Chem. Int. Ed. 2018, 57, 5492–5496.
(21) Cao, Y.–X.; Dong, X.–Y.; Yang, J.; Jiang, S.–P.; Zhou, S.;
Li, Z.–L.; Chen, G.–Q.; Liu, X.–Y. A Copper–Catalyzed So‐
nogashira Coupling Reaction of Diverse Activated Alkyl
Halides with Terminal Alkynes Under Ambient Condi‐
tions. Adv. Synth. Catal. 2020, 362, 2280–2284.
(22) Lang, H.; Jakob, A.; Milde, B. Copper(I) Alkyne and Al‐
kynide Complexes. Organometallics 2012, 31, 7661−7693.
(23) Zhang, Q.; Wang, T.; Zhang, X.; Tong, S.; Wu, Y.–D.;
Wang, M.–X. Radical Reactivity, Catalysis, and Reaction
Mechanism of Arylcopper(II) Compounds: The Missing
Link in Organocopper Chemistry. J. Am. Chem. Soc. 2019,
141, 18341−18348.
Author Contributions
‡These authors contributed equally.
ACKNOWLEDGMENT
We are grateful for support by the US National Science
Foundation (CHE‐1665348) and the Georgetown Environ‐
ment Initiative (T.H.W.).
REFERENCES
(1) Knochel, P.; Molander, G. A. Comprehensive Organic Syn‐
thesis 2nd edn. Elsevier, Amsterdam, The Netherlands,
2014.
(2) Glaser, C. Beiträge zur Kenntniss des Acetenylbenzols.
Chem. Ber. 1869, 2, 422–424.
(3) Salkind, J. S.; Fundyler, F. B. A New Synthesis of Diacety‐
lenderivative. Chem. Ber. 1936, 69, 128–130.
(4) Bohlmann, F.; Schönowsky, H.; Inhoffen, E; Grau, G.
Polyacetylenverbindungen, LII. Über den Mechanismus
der
Öxydativen
Dimerisierung
von
Acetylen‐
verbindungen, Chem. Ber. 1964, 97, 794–800.
(5) Vilhelmsen, M. H.; Jensen, J.; Tortzen, C. G.; Nielsen, M.
B. The Glaser–Hay Reaction: Optimization and Scope
Based on 13C NMR Kinetics Experiments. Eur. J. Org.
Chem. 2013, 701–711.
(6) Hay, A. S. Oxidative Coupling of Acetylenes. II. J. Org.
Chem. 1962, 27, 3320–3321.
(7) Van Koten, G.; James, S. L.; Jastrzebski, J. T. B. H. Copper
and Silver. Comprehensive Organometallic Chemistry II.,
1995, 57–133.
(8) Dong, X‐Y.; Zhang, Y.‐F.; Ma,; C.‐L.; Gu, Q.‐S.; Wang, F‐
L.; Li, Z.‐L.; Jiang, S.‐P.; Liu, X.‐Y. A General Asymmetric
Copper‐Catalyzed Sonogashira C(sp3)–C(sp) Coupling.
Nat. Chem. 2019, 11, 1158–1166.
(9) Fu, L.; Zhou, S.; Wan, X.; Chen, P.; Liu, G. Enantioselec‐
tive Trifluoromethylalkynylation of Alkenes via Copper–
Catalyzed Radical Relay. J. Am. Chem. Soc. 2018, 140,
10965–10969.
(10) Zhu, L.; Brassard, C. J.; Zhang, X.; Guha P. M.; Clark, R. J.
On the Mechanism of Copper(I)–Catalyzed Azide‐Alkyne
Cycloaddition. Chem. Rec. 2016, 16, 1501–1517.
(11) Tang, S.; Liu, Y.; Gao, X.; Wang, P.; Huang, P.; Lei, A.
Multi–Metal–Catalyzed Oxidative Radical Alkynylation
with Terminal Alkynes: A New Strategy for C(sp3)–C(sp)
Bond Formation. J. Am. Chem. Soc. 2018, 140, 6006–6013.
(12) Tang, S.; Wang, P.; Li, H.; Lei, A. Multimetallic Catalysed
Radical Oxidative C(sp3)–H/C(sp)–H Cross‐Coupling Be‐
tween Unactivated Alkanes and Terminal Alkynes. Nat.
Commun. 2016, 7, 11676.
(24) Ziegler, M. S.; Lakshmi, K. V.; Tilley, T. D. Dicopper
Cu(I)Cu(I) and Cu(I)Cu(II) Complexes in Copper–
Catalyzed Azide–Alkyne Cycloaddition. J. Am. Chem. Soc.
2017, 139, 5378−5386.
(25) Kundu, S.; Greene, C.; Williams, K. D.; Salvador, T. K.;
Bertke, J. A.; Cundari, T. R.; Warren, T. H. Three‐
Coordinate Copper(II) Aryls: Key Intermediates in C–O
Bond Formation. J. Am. Chem. Soc. 2017, 139, 9112–9115.
(26) Bakhoda, A.; Jiang, Q.; Bertke, J. A.; Cundari, T. R.; War‐
ren, T. H. Elusive Terminal Copper Arylnitrene Interme‐
diates. Angew. Chem. Int. Ed. 2017, 56, 6426–6430.
(27) Wiese, S.; Badiei, Y. M.; Gephart, R. T.; Mossin, S.; Va‐
ronka, M. S.; Melzer, M. M.; Meyer, K.; Cundari, T. R.;
Warren, T. H. C‐H Amination with Unactivated Amines
Through Copper(II) Amides. Angew. Chem. Int. Ed. 2010,
49, 8850–8855.
(28) Melzer, M. M.; Mossin, S.; Cardenas, A. J. P.; Williams, K.
D.; Zhang, S.; Meyer, K.; Warren, T. H. A Copper(II) Thi‐
olate from Reductive Cleavage of an S‐Nitrosothiol. In‐
org. Chem. 2012, 51, 8658–8660.
(29) Salvador, T. K.; Arnett, C. H.; Kundu, S. K.; Sapiezynski,
N. G.; Bertke, J. A.; Raghibi Boroujeni, M.; Warren, T. H.
Copper Catalyzed sp3 C–H Etherification with Acyl Pro‐
tected Phenols. J. Am. Chem. Soc. 2016, 138, 16580–16583.
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