- Refining boron-iodane exchange to access versatile arylation reagents
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Aryl(Mes)iodonium salts, which are multifaceted aryl transfer reagents, are synthesized via boron-iodane exchange. Modification to both the nucleophilic (aryl boron) and electrophilic (mesityl-λ3-iodane) reaction components results in improved yield and faster reaction time compared to previous conditions. Mechanistic studies reveal a pathway that is more like transmetallation than SEAr.
- Karandikar, Shubhendu S.,Stuart, David R.
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supporting information
p. 1211 - 1214
(2022/02/03)
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- Scalable electrochemical synthesis of diaryliodonium salts
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Cyclic and acyclic diaryliodonium are synthesised by anodic oxidation of iodobiaryls and iodoarene/arene mixtures, respectively, in a simple undivided electrolysis cell in MeCN-HFIP-TfOH without any added electrolyte salts. This atom efficient process does not require chemical oxidants and generates no chemical waste. More than 30 cyclic and acyclic diaryliodonium salts with different substitution patterns were prepared in very good to excellent yields. The reaction was scaled-up to 10 mmol scale giving more than four grams of dibenzo[b,d]iodol-5-ium trifluoromethanesulfonate (>95%) in less than three hours. The solvent mixture of the large-scale experiment was recovered (>97%) and recycled several times without significant reduction in yield.
- Elsherbini, Mohamed,Moran, Wesley J.
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supporting information
p. 4706 - 4711
(2021/06/11)
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- Synthesis of Diverse Aryliodine(III) Reagents by Anodic Oxidation?
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An anodic oxidation enabled synthesis of hypervalent iodine(III) reagents from aryl iodides is demonstrated. Under mild electrochemical conditions, a range of aryliodine(III) reagents including iodosylarenes, (difunctionaliodo)arenes, benziodoxoles and diaryliodonium salts can be efficiently synthesized and derivatized in good to excellent yields with high selectivity. As only electrons serve as the oxidation reagents, this method offers a more straightforward and sustainable manner avoiding the use of expensive or hazardous chemical oxidants.
- Zu, Bing,Ke, Jie,Guo, Yonghong,He, Chuan
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supporting information
p. 627 - 632
(2021/02/12)
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- Versatile and base-free copper-catalyzed α-arylations of aromatic ketones using diaryliodonium salts
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A ligand and base-free copper catalyzed synthetic method for the efficient α-arylation of aromatic ketones is described. In order to avoid strong bases, ketone-derived silyl enol ethers were employed. Their reaction with diaryliodonium salts as aryl source provided the intermolecular C–C coupling displaying good functional group tolerance and requiring low catalyst loading.
- Bouquin, Maxime,Jaroschik, Florian,Taillefer, Marc
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supporting information
(2021/06/11)
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- Flow Synthesis of Diaryliodonium Triflates
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A safe and scalable synthesis of diaryliodonium triflates was achieved using a practical continuous-flow design. A wide array of electron-rich to electron-deficient arenes could readily be transformed to their respective diaryliodonium salts on a gram scale, with residence times varying from 2 to 60 s (44 examples).
- Laudadio, Gabriele,Gemoets, Hannes P. L.,Hessel, Volker,No?l, Timothy
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p. 11735 - 11741
(2017/11/24)
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- A Modular Flow Design for the meta-Selective C?H Arylation of Anilines
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Described herein is an effective and practical modular flow design for the meta-selective C?H arylation of anilines. The design consists of four continuous-flow modules (i.e., diaryliodonium salt synthesis, meta-selective C?H arylation, inline copper extraction, and aniline deprotection) which can be operated either individually or consecutively to provide direct access to meta-arylated anilines. With a total residence time of 1 hour, the desired product could be obtained in high yield and excellent purity without the need for column chromatography, and the residual copper content meets the standards for parenterally administered pharmaceutical substances.
- Gemoets, Hannes P. L.,Laudadio, Gabriele,Verstraete, Kirsten,Hessel, Volker,No?l, Timothy
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supporting information
p. 7161 - 7165
(2017/06/13)
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- Facile One-Pot Synthesis of Diaryliodonium Salts from Arenes and Aryl Iodides with Oxone
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A straightforward synthesis of diaryliodonium salts is achieved by using Oxone as the stoichiometric oxidant. Slow addition is the key to obtaining good yields and purities of the reaction products, which are highly useful reagents in many different areas of organic synthesis.
- Soldatova, Natalia,Postnikov, Pavel,Kukurina, Olga,Zhdankin, Viktor V.,Yoshimura, Akira,Wirth, Thomas,Yusubov, Mekhman S.
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- A Modular Synthesis of 4-Aminoquinolines and [1,3] N-to-C Rearrangement to Quinolin-4-ylmethanesulfonamides
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A copper-catalyzed regiocontrolled three-component reaction afforded diversified 4-aminoquinolines using nitriles, diaryliodoniums, and ynamides. The C7-substituted regioisomers were formed regioselectively when meta-substituted phenyliodonium salts were used. [1,3] N-to-C rearrangement of the products to quinolin-4-ylmethanesulfonamides and simultaneous deprotection of benzyl and sulfonamide group were newly developed. Finally, antimalarial CK-2-68 was successfully prepared.
- Oh, Kyung Hwan,Kim, Jin Gyeong,Park, Jin Kyoon
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supporting information
p. 3994 - 3997
(2017/08/14)
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- Synthesis of quaternary aryl phosphonium salts: Photoredox-mediated phosphine arylation
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We report a synthesis method for the construction of quaternary aryl phoshonium salts at ambient temperature. The regiospecific reaction involves the coupling of phosphines with aryl radicals derived from diaryliodonium salts under photoredox conditions.
- Fearnley,An,Jackson,Lindovska,Denton
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supporting information
p. 4987 - 4990
(2016/04/08)
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- Copper-catalyzed oxidative ring closure of ortho-cyanoanilides with hypervalent iodonium salts: Arylation-ring closure approach to iminobenzoxazines
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A novel, highly modular synthetic methodology with high functional group tolerance was developed for the construction of iminobenzoxazine derivatives from ortho-cyanoanilides and diaryliodonium triflates via an oxidative arylation-cyclization path. The reaction is supposed to involve the formation of highly active aryl-copper(III) species. In this novel transformation, copper(II) triflate was used as catalyst in 1,2-dichloroethane or ethyl acetate and the reaction takes place at 75 °C in 2-16 h.
- Aradi, Klra,Novk, Zoltn
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supporting information
p. 371 - 376
(2015/03/05)
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- Utilization of Copper-Catalyzed Carboarylation-Ring Closure for the Synthesis of New Oxazoline Derivatives
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A copper-catalyzed carboarylation-ring-closure strategy was used for the modular synthesis of oxazolines via the reaction of 1-aryl- and 1-alkylpropargylamides and diaryliodonium salts. The novel approach enables the efficient, modular synthesis of oxazol
- Sinai, ádám,Vangel, Dóra,Gáti, Tamás,Bombicz, Petra,Novák, Zoltán
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supporting information
p. 4136 - 4139
(2015/09/15)
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- Transition-Metal-Free N-Arylation of Pyrazoles with Diaryliodonium Salts
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A new synthetic method was developed for the N-arylation of pyrazoles using diaryliodonium salts. The transformation does not require any transition-metal catalyst and provides the desired N-arylpyrazoles rapidly under mild reaction condition in the presence of aqueous ammonia solution as a mild base without the use of inert atmosphere. The chemoselectivity of unsymmetric diaryliodonium salts was also explored with large number of examples.
- Gonda, Zsombor,Novák, Zoltán
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supporting information
p. 16801 - 16806
(2015/11/16)
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- Palladium-catalyzed P(O)R2 directed C-H arylation to synthesize electron-rich polyaromatic monophosphorus ligands
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Palladium-catalyzed arylation of (diisopropylphosphoryl)biphenyl skeleton derivatives by the P(O)R2 directed C-H functionalization was reported. The related products were obtained in high regioselectivity and good functional group tolerance was observed. This reaction provided a new and efficient pathway for the synthesis of polyaromatic monophosphorus ligands. The Royal Society of Chemistry.
- Hu, Rong-Bin,Zhang, Heng,Zhang, Xiao-Yu,Yang, Shang-Dong
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supporting information
p. 2193 - 2195
(2014/02/14)
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- Copper-catalyzed oxidative electrophilic carbofunctionalization of acrylamides for the synthesis of oxindoles
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A novel and efficient copper-catalyzed tandem oxidative cyclization of arylacrylamides with diaryliodonium salts is reported. This reaction provides a novel approach for the synthesis of oxindoles and various functional groups were well tolerated.
- Li, Xueqin,Xu, Jian,Zhang, Pengbo,Gao, Yuzhen,Wu, Ju,Tang, Guo,Zhao, Yufen
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supporting information
p. 2009 - 2012
(2014/11/08)
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- Copper-catalyzed oxidative ring closure and carboarylation of 2-ethynylanilides
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A new copper-catalyzed oxidative ring closure of ethynyl anilides with diaryliodonium salts was developed for the highly modular construction of benzoxazines bearing a fully substituted exo double bond. The oxidative transformation includes an unusual 6-exo-dig cyclization step with the formation of C-O and C-C bonds.
- Sinai, Adam,Meszaros, Adam,Gati, Tamas,Kudar, Veronika,Pallo, Anna,Novak, Zoltan
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supporting information
p. 5654 - 5657
(2013/12/04)
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- Halogen exchange via a halogenation of diaryliodonium salts with cuprous halide
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An efficient halogenation reaction has been developed with diaryliodonium salts and cuprous halides. Various diaryliodonium salts 1 could perform the reaction with readily available CuBr or CuCl in CH3CN at 80°C, assembling bromoarenes or chloroarenes in up to 92% yields. This provides us a method for the transformation from iodoarenes to other haloarenes.
- Li, Jian,Liu, Li,Ding, Dong,Sun, Jiang-Tao
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p. 541 - 548
(2014/01/06)
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- Enantioselective α-arylation of N-acyloxazolidinones with copper(II)-bisoxazoline catalysts and diaryliodonium salts
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A new strategy for the catalytic enantioselective α-arylation of N-acyloxazolidinones with chiral copper(II)-bisoxazoline complexes and diaryliodonium salts is described. The mild catalytic conditions are operationally simple, produce valuable synthetic building blocks in excellent yields and enantioselectivities, and can be applied to the synthesis of important nonsteroidal anti-inflammatory agents and their analogues.
- Bigot, Aurelien,Williamson, Alice E.,Gaunt, Matthew J.
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experimental part
p. 13778 - 13781
(2011/10/09)
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- Enantioselective α-arylation of aldehydes via the productive merger of iodonium salts and organocatalysis
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The enantioselective α-arylation of aldehydes has been accomplished using diaryliodonium salts and a combination of copper and organic catalysts. These mild catalytic conditions provide a new strategy for the enantioselective construction and retention of enolizable α-formyl benzylic stereocenters, a valuable synthon for the production of medicinal agents. As one example, this new asymmetric protocol has been applied to the rapid synthesis of (S)-ketoprofen, a commercially successful oral and topical analgesic.
- Allen, Anna E.,MacMillan, David W. C.
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supporting information; experimental part
p. 4260 - 4263
(2011/06/21)
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