84563-54-2Relevant academic research and scientific papers
Transition Metal-Free N-Arylation of Amino Acid Esters with Diaryliodonium Salts
Kervefors, Gabriella,Kersting, Leonard,Olofsson, Berit
supporting information, p. 5790 - 5795 (2021/03/08)
A transition metal-free approach for the N-arylation of amino acid derivatives has been developed. Key to this method is the use of unsymmetric diaryliodonium salts with anisyl ligands, which proved important to obtain high chemoselectivity and yields. The scope includes the transfer of both electron deficient, electron rich and sterically hindered aryl groups with a variety of different functional groups. Furthermore, a cyclic diaryliodonium salt was successfully employed in the arylation. The N-arylated products were obtained with retained enantiomeric excess.
N1- and N3-Arylations of Hydantoins Employing Diaryliodonium Salts via Copper(I) Catalysis at Room Temperature
Abha Saikia, Raktim,Barman, Dhiraj,Dutta, Anurag,Jyoti Thakur, Ashim
supporting information, p. 400 - 410 (2020/12/17)
Copper(I)-catalyzed N-arylation (both N1- and N3-) of hydantoins with diaryliodonium salts as aryl partners at room temperature is reported. The transformation allows diverse scopes on both hydantoins and diaryliodonium salts deliver
Direct Copper-Catalyzed C-3 Arylation of Diphenylphosphine Oxide Indoles
Huang, Xiao-Ling,Li, Chong,Wang, Juan,Yang, Shang-Dong
supporting information, (2021/10/25)
We have developed a simple and effective method for the C-3 arylation of phosphorus-containing indole compounds in the presence of CuI under mild conditions. This reaction provides a reliable method for the modification of ligands.
Copper-catalyzed arylation of polycyclic aromatic hydrocarbons by the PO group
Niu, Yuan,Qi, Zhichao,Lou, Qinxin,Bai, Pengbo,Yang, Shangdong
, p. 14721 - 14724 (2020/12/02)
The first example of a directed and regioselective arylation of polycyclic aromatic hydrocarbons (PAHs) by using a PO directing group is reported herein. The protocol uses a cheap copper catalyst, and results in a breakthrough meta-selective C-H functionalization of arylphosphine oxide compounds. Substrates with potential fluorescence properties, for example, pyrene and fluoranthene, were successfully arylated under the system, thus achieving an efficient modification of fluorescent molecules containing the PO functional group. This journal is
Spatial anion control on palladium for mild C-H arylation of arenes
Dhankhar, Jyoti,González-Fernández, Elisa,Dong, Chao-Chen,Mukhopadhyay, Tufan K.,Linden, Anthony,?ori?, Ilija
supporting information, p. 19040 - 19046 (2020/11/13)
C-H arylation of arenes without the use of directing groups is a challenge, even for simple molecules, such as benzene. We describe spatial anion control as a concept for the design of catalytic sites for C-H bond activation, thereby enabling nondirected C-H arylation of arenes at ambient temperature. The mild conditions enable late-stage structural diversification of biologically relevant small molecules, and site-selectivity complementary to that obtained with other methods of arene functionalization can be achieved. These results reveal the potential of spatial anion control in transition-metal catalysis for the functionalization of C-H bonds under mild conditions.
Palladium(ii)-catalyzed stereoselective synthesis of: C-glycosides from glycals with diaryliodonium salts
Das, Mrinmoy,Lee, Jiande,Liu, Xue-Wei,Pal, Kumar Bhaskar
supporting information, p. 2242 - 2251 (2020/04/07)
An efficient palladium(ii) mediated C-glycosylation of glycals with diaryliodonium salts is described, providing a new strategy for the synthesis of 2,3-dideoxy C-Aryl glycosides with excellent stereoselectivity. The C-glycosylation of a diverse range of
Lewis Acidity Scale of Diaryliodonium Ions toward Oxygen, Nitrogen, and Halogen Lewis Bases
Legault, Claude Y.,Mayer, Robert J.,Mayr, Herbert,Ofial, Armin R.
supporting information, (2020/03/13)
Equilibrium constants for the associations of 17 diaryliodonium salts Ar2I+X- with 11 different Lewis bases (halide ions, carboxylates, p-nitrophenolate, amines, and tris(p-anisyl)phosphine) have been investigated by titrations followed by photometric or conductometric methods as well as by isothermal titration calorimetry (ITC) in acetonitrile at 20 °C. The resulting set of equilibrium constants KI covers 6 orders of magnitude and can be expressed by the linear free-energy relationship lg KI = sI LAI + LBI, which characterizes iodonium ions by the Lewis acidity parameter LAI, as well as the iodonium-specific affinities of Lewis bases by the Lewis basicity parameter LBI and the susceptibility sI. Least squares minimization with the definition LAI = 0 for Ph2I+ and sI = 1.00 for the benzoate ion provides Lewis acidities LAI for 17 iodonium ions and Lewis basicities LBI and sI for 10 Lewis bases. The lack of a general correlation between the Lewis basicities LBI (with respect to Ar2I+) and LB (with respect to Ar2CH+) indicates that different factors control the thermodynamics of Lewis adduct formation for iodonium ions and carbenium ions. Analysis of temperature-dependent equilibrium measurements as well as ITC experiments reveal a large entropic contribution to the observed Gibbs reaction energies for the Lewis adduct formations from iodonium ions and Lewis bases originating from solvation effects. The kinetics of the benzoate transfer from the bis(4-dimethylamino)-substituted benzhydryl benzoate Ar2CH-OBz to the phenyl(perfluorophenyl)iodonium ion was found to follow a first-order rate law. The first-order rate constant kobs was not affected by the concentration of Ph(C6F5)I+ indicating that the benzoate release from Ar2CH-OBz proceeds via an unassisted SN1-type mechanism followed by interception of the released benzoate ions by Ph(C6F5)I+ ions.
Synthesis of phenols and aryl silyl ethers via arylation of complementary hydroxide surrogates
Reitti, Marcus,Gurubrahamam, Ramani,Walther, Melanie,Lindstedt, Erik,Olofsson, Berit
supporting information, p. 1785 - 1788 (2018/04/14)
Two transition-metal-free methods to access substituted phenols via the arylation of silanols or hydrogen peroxide with diaryliodonium salts are presented. The complementary reactivity of the two nucleophiles allows synthesis of a broad range of phenols without competing aryne formation, as illustrated by the synthesis of the anesthetic Propofol. Furthermore, silyl-protected phenols can easily be obtained, which are suitable for further transformations.
Regiospecific N-Arylation of Aliphatic Amines under Mild and Metal-Free Reaction Conditions
Purkait, Nibadita,Kervefors, Gabriella,Linde, Erika,Olofsson, Berit
supporting information, p. 11427 - 11431 (2018/08/28)
A transition metal-free N-arylation of primary and secondary amines with diaryliodonium salts is presented. Both acyclic and cyclic amines are well tolerated, providing a large set of N-alkyl anilines. The methodology is unprecedented among metal-free methods in terms of amine scope, the ability to transfer both electron-withdrawing and electron-donating aryl groups, and efficient use of resources, as excess substrate or reagents are not required.
Transition metal-free, chemoselective arylation of thioamides yielding aryl thioimidates or N-aryl thioamides
Villo, Piret,Kervefors, Gabriella,Olofsson, Berit
, p. 8810 - 8813 (2018/08/17)
Reactions of secondary thioamides with diaryliodonium salts under basic, transition metal-free conditions resulted in chemoselective S-arylation to provide aryl thioimidates in good to excellent yields. Equimolar amounts of thioamide, base and diaryliodonium salt were sufficient to obtain a diverse selection of products within short reaction times. Reactions with thiolactams delivered N-arylated thioamides in good yield at room temperature.
