Organic Letters
Letter
Cross-Coupling with Aryldiazonium Salts: Redox Gold Catalysis
without an External Oxidant. Angew. Chem., Int. Ed. 2015, 54, 8772−
8776. (b) Levin, M. D.; Toste, F. D. Gold-Catalyzed Allylation of Aryl
Boronic Acids: Accessing Cross-Coupling Reactivity with Gold.
Angew. Chem., Int. Ed. 2014, 53, 6211−6215. (c) Hashmi, A. S. K.;
Notes
The authors declare no competing financial interest.
Lothschutz, C.; Dopp, R.; Ackermann, M.; De Becker, J. D.; Rudolph,
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ACKNOWLEDGMENTS
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M.; Scholz, C.; Rominger, F. On Homogeneous Gold/Palladium
Catalytic Systems. Adv. Synth. Catal. 2012, 354, 133−147. (d) Witzel,
S.; Xie, J.; Rudolph, M.; Hashmi, A. S. K. Photosensitizer-Free, Gold-
Catalyzed C-C Cross-Coupling of Boronic Acids and Diazonium Salts
Enabled by Visible Light. Adv. Synth. Catal. 2017, 359, 1522−1528.
(12) Johnson, M. W.; Bagley, S. W.; Mankad, N. P.; Bergman, R. G.;
Mascitti, V.; Toste, F. D. Application of Fundamental Organometallic
Chemistry to the Development of a Gold-Catalyzed Synthesis of
Sulfinate Derivatives. Angew. Chem., Int. Ed. 2014, 53, 4404−4407.
(13) (a) Zhu, H.; Shen, Y.; Deng, Q.; Chen, J.; Tu, T.
Acenaphthoimidazolylidene Gold Complex-Catalyzed Alkylsulfonyla-
tion of Boronic Acids by Potassium Metabisulfite and Alkyl Halides: A
Direct and Robust Protocol to Access Sulfones. ACS Catal. 2017, 7,
4655−4659. (b) Zhu, H.; Shen, Y.; Deng, Q.; Chen, J.; Tu, T.
Pd(NHC)-Catalyzed Alkylsulfonylation of Boronic Acids: A General
and Efficient Approach for Sulfone Synthesis. Chem. Commun. 2017,
53, 12473−12476.
Financial support from the National Key R&D Program of
China (No. 2016YFA0202902), the National Natural Science
Foundation of China (Nos. 21572036, 21871059, 21801040,
and 21861132002), Youth Foundation of Jiangxi Educational
Committee (GJJ170432), and the Department of Chemistry at
Fudan University is gratefully acknowledged.
REFERENCES
■
(1) (a) Yang, Y.; Lan, J.; You, J. Palladium-Catalyzed Trans-
formations of Alkyl C-H Bonds. Chem. Rev. 2017, 117, 8787−8863.
(b) Liu, L.; Zhang, J. Gold-Catalyzed Transformations of α-
Diazocarbonyl Compounds: Selectivity and Diversity. Chem. Soc.
Rev. 2016, 45, 506−516. (c) Liu, C.; Zhang, H.; Shi, W.; Lei, A. Bond
Formations between Two Nucleophiles: Transition Metal Catalyzed
Oxidative Cross-Coupling Reactions. Chem. Rev. 2011, 111, 1780−
1824.
(14) (a) Aziz, J.; Messaoudi, S.; Alami, M.; Hamze, A. Sulfinate
Derivatives: Dual and Versatile Partners in Organic Synthesis. Org.
Biomol. Chem. 2014, 12, 9743−9759. (b) Zhao, F.; Tan, Q.; Xiao, F.;
Zhang, S.; Deng, G.-J. Palladium-Catalyzed Desulfitative Cross-
Coupling Reaction of Sodium Sulfinates with Benzyl Chlorides.
Org. Lett. 2013, 15, 1520−1523.
(15) Merritt, E. A.; Olofsson, B. Diaryliodonium Salts: A Journey
from Obscurity to Fame. Angew. Chem., Int. Ed. 2009, 48, 9052−9070.
(16) (a) Deprez, N. R.; Sanford, M. S. Synthetic and Mechanistic
Studies of Pd-Catalyzed C-H Arylation with Diaryliodonium Salts:
Evidence for a Bimetallic High Oxidation State Pd Intermediate. J.
Am. Chem. Soc. 2009, 131, 11234−11241. (b) Jalalian, N.; Ishikawa,
E. E.; Silva, L. F. J.; Olofsson, B. Room Temperature, Metal-Free
Synthesis of Diaryl Ethers with Use of Diaryliodonium Salts. Org. Lett.
2011, 13, 1552−1555. (c) Wang, M.; Fan, Q.; Jiang, X. Nitrogen-
Iodine Exchange of Diaryliodonium Salts: Access to Acridine and
Carbazole. Org. Lett. 2018, 20, 216−219. (d) Purkait, N.; Kervefors,
G.; Linde, E.; Olofsson, B. Regiospecific N-Arylation of Aliphatic
Amines under Mild and Metal-Free Reaction Conditions. Angew.
Chem., Int. Ed. 2018, 57, 11427−11431.
(2) (a) Yin, J.; Rainka, M. P.; Zhang, X.-X.; Buchwald, S. L. A Highly
Active Suzuki Catalyst for the Synthesis of Sterically Hindered Biaryls:
Novel Ligand Coordination. J. Am. Chem. Soc. 2002, 124, 1162−1163.
(b) Dai, C.; Fu, G. C. The First General Method for Palladium-
Catalyzed Negishi Cross-Coupling of Aryl and Vinyl Chlorides: Use
of Commercially Available Pd(P(t-Bu)3)2 as a Catalyst. J. Am. Chem.
Soc. 2001, 123, 2719−2724.
(3) Walker, S. D.; Barder, T. E.; Martinelli, J. R.; Buchwald, S. L. A
Rationally Designed Universal Catalyst for Suzuki-Miyaura Coupling
Processes. Angew. Chem., Int. Ed. 2004, 43, 1871−1876.
(4) (a) Altenhoff, G.; Goddard, R.; Lehmann, C. W.; Glorius, F.
Sterically Demanding, Bioxazoline-Derived N-Heterocyclic Carbene
Ligands with Restricted Flexibility for Catalysis. J. Am. Chem. Soc.
2004, 126, 15195−15201. (b) Tu, T.; Sun, Z.; Fang, W.; Xu, M.;
Zhou, Y. Robust Acenaphthoimidazolylidene Palladium Complexes:
Highly Efficient Catalysts for Suzuki-Miyaura Couplings with
Sterically Hindered Substrates. Org. Lett. 2012, 14, 4250−4253.
(5) (a) Dong, K.; Wu, X.-F. Carbonylations with CO2 as the CO
Source and Reactivity Modifier. Angew. Chem., Int. Ed. 2017, 56,
5399−5401. (b) Lian, Z.; Nielsen, D. U.; Lindhardt, A. T.; Daasbjerg,
K.; Skrydstrup, T. Cooperative Redox Activation for Carbon Dioxide
Conversion. Nat. Commun. 2016, 7, 13782−13788. (c) Friis, S. D.;
Lindhardt, A. T.; Skrydstrup, T. The Development and Application of
Two-Chamber Reactors and Carbon Monoxide Precursors for Safe
Carbonylation Reactions. Acc. Chem. Res. 2016, 49, 594−605.
(d) Fang, W.; Zhu, H.; Deng, Q.; Liu, S.; Liu, X.; Shen, Y.; Tu, T.
Design and Development of Ligands for Palladium-Catalyzed
Carbonylation Reactions. Synthesis 2014, 46, 1689−1708.
(6) Ma, Y.; Liu, R.; Gong, X.; Li, Z.; Huang, Q.; Wang, H.; Song, G.
Synthesis and Herbicidal Activity of N,N-Diethyl-3-(arylselenonyl)-
1H-1,2,4-triazole-1-carboxamide. J. Agric. Food Chem. 2006, 54,
7724−7728.
(7) Zhu, H.; Shen, Y.; Deng, Q.; Tu, T. Copper-catalyzed
Electrophilic Amination of Sodium Sulfinates at Room Temperature.
Chem. Commun. 2015, 51, 16573−16576.
(8) Umierski, N.; Manolikakes, G. Metal-Free Synthesis of Diaryl
Sulfones from Arylsulfinic Acid Salts and Diaryliodonium Salts. Org.
Lett. 2013, 15, 188−191.
(9) Emmett, E. J.; Hayter, B. R.; Willis, M. C. Palladium-Catalyzed
Three-Component Diaryl Sulfone Synthesis Exploiting the Sulfur
Dioxide Surrogate DABSO. Angew. Chem., Int. Ed. 2013, 52, 12679−
12683.
(10) Chen, Y.; Willis, M. C. Copper(I)-Catalyzed Sulfonylative
Suzuki−Miyaura Cross-Coupling. Chem. Sci. 2017, 8, 3249−3253.
(11) (a) Cai, R.; Lu, M.; Aguilera, E. Y.; Xi, Y.; Akhmedov, N. G.;
Petersen, J. L.; Chen, H.; Shi, X. Ligand-Assisted Gold-Catalyzed
(17) Kalyani, D.; Deprez, N. R.; Desai, L. V.; Sanford, M. S.
Oxidative C-H Activation/C-C Bond Forming Reactions: Synthetic
Scope and Mechanistic Insights. J. Am. Chem. Soc. 2005, 127, 7330−
7331.
(18) (a) Jiang, J.; Zhu, H.; Shen, Y.; Tu, T. Acenaphthoimidazolium
Chloride-Enabled Nickel-Catalyzed Amination of Bulky Aryl
Tosylates. Org. Chem. Front. 2014, 1, 1172−1175. (b) Liu, Z.;
Dong, N.; Xu, M.; Sun, Z.; Tu, T. Mild Negishi Cross-Coupling
Reactions Catalyzed by Acenaphthoimidazolylidene Palladium
Complexes at Low Catalyst Loadings. J. Org. Chem. 2013, 78,
7436−7444. (c) Tu, T.; Fang, W.; Jiang, J. A Highly Efficient
Precatalyst for Amination of Aryl Chlorides: Synthesis, Structure and
Application of a Robust Acenaphthoimidazolylidene Palladium
Complex. Chem. Commun. 2011, 47, 12358−12360.
(19) (a) Nguyen, B.; Emmett, E. J.; Willis, M. C. Palladium-
Catalyzed Aminosulfonylation of Aryl Halides. J. Am. Chem. Soc.
2010, 132, 16372−16373. (b) Emmett, E. J.; Hayter, B. R.; Willis, M.
C. Palladium-Catalyzed Synthesis of Ammonium Sulfinates from Aryl
Halides and a Sulfur Dioxide Surrogate: A Gas- and Reductant-Free
Process. Angew. Chem., Int. Ed. 2014, 53, 10204−10208. (c) Shavnya,
A.; Hesp, K. D.; Mascitti, V.; Smith, A. C. Palladium-Catalyzed
Synthesis of (Hetero)Aryl Alkyl Sulfones from (Hetero)Aryl Boronic
Acids, Unactivated Alkyl Halides, and Potassium Metabisulfite. Angew.
Chem., Int. Ed. 2015, 54, 13571−13575. (d) Wang, X.; Xue, L.; Wang,
Z. A Copper-Catalyzed Three-Component Reaction of Triethox-
E
Org. Lett. XXXX, XXX, XXX−XXX