Copper-catalyzed direct oxidation and N-arylation of benzylamines with diaryliodonium salts

<正>1 The study of reaction conditions Table S1 The optimization of the rate of copper slats and ligand a) Entry Anion Cu/ligand Yield b)(%) 1 2 3 OTf OTf OTf 10%:20% 10%:10% 5%:10% 91 65 45 a) Reaction conditions: 1a(0.60 mmol), 2a(0.20 mmol), Cu(OTf)2(x mol%), K2CO3(2.5 equiv.), 1,10-phenanthroline(y mol%), DMSO(2 mL), 150 °C, 24 h; b) isolated yields. Table S2 The optimization of the substrates' rate a) Entry 1a/2a(mmol) Yield b)(%) 1 2 3 4 5 6 0.2:0.2 0.2:0.24 0.2:0.4 0.6:0.2 0.4:0.2 1.0:0.2 54 60 58 91 73 83 a) Reaction conditions: 1a(x mmol), 2a(y mmol), Cu(OTf)2(10 mol%), K2CO3(2.5 equiv.), 1,10-phenanthroline(20 mol%), DMSO(2 mL), 150 °C, 24 h; b) isolated yields.     

2-炔基苯胺与二芳基碘鎓盐的选择性芳基化/环化串联反应

有机高价碘试剂是一类环境友好、制备简单且性质温和的有机合成新试剂。近年来,有机高价碘试剂因表现出新颖、独特的反应性能而受到化学工作者广泛关注,成为有机合成重要研究领域之一。二芳基碘鎓盐是有机高价碘试剂的一个重要组成部分,是一类具有较高普适性的芳基化试剂,可用于羰基化合物、烯烃、炔烃和杂原子亲核化合物等的芳基化反应。目前,二芳基碘鎓盐作为芳基化试剂对具有单一芳基化位点化合物的芳基化已经有了非常广泛而深入的研究。对于具有两个甚至多个芳基化位点的化合物(如同时具有胺基和炔基),其芳基化选择性问题仍缺乏系统研究。特别是在多个芳基化位点共存时如何能够使芳基化发生在某一特定位点仍然是一大难题。这限制了二芳基碘鎓盐作为芳基化试剂更广泛的应用。因此,我们选用2-炔基苯胺(含有胺基和炔基两个芳基化位点)作为原料,通过溶剂的选择以及溶液酸碱性的调控来改变不同芳基化位点的反应活性,通过催化剂的调变来改变二芳基碘鎓盐芳基化反应的能力,从而找出最优条件实现底物分子的选择性芳基化反应,并利用剩余活性位点实现分子内的环化反应,从而实现芳基化-环化串联反应合成一系列N-芳基吲哚类化合物。在对模型底物进行条件筛选实验时发现,以2-乙基辛酸铜(Cu(OCOC8H17)2)作催化剂,二异丙基乙基胺(DIPEA)作碱,1,2-二氯乙烷(DCE)为溶剂,反应以最高93%的收率得到1,2-二苯基吲哚。使用该最优反应条件,一系列2-炔基苯胺都能与二芳基碘鎓盐很好地发生反应并且以良好到优秀的产率(71%–98%)得到目标产物N-芳基吲哚。此外,2-炔基苯胺与非对称的二芳基碘鎓盐也能发生反应,实验结果证明为位阻较小的芳基对胺基进行了N-芳基化反应。通过空白实验和对比实验,我们提出了可能的反应机理：二芳基碘鎓盐在铜催化剂作用下转化为亲电性的芳基活性中间体,该中间体与底物的胺基发生芳基化反应,然后芳基化产物在铜催化剂作用下环化生成N-芳基吲哚。该反应很好地解决了同时具有胺基和炔基两个芳基化位点的底物与二芳基碘鎓盐反应时C-芳基化和N-芳基化的竞争问题,选择合适反应条件使N-芳基化反应优先进行,为二芳基碘鎓盐的选择性芳基化反应提供了很好的实例,并为其它具有多个芳基化位点化合物的选择性芳基化反应提供了途径。     

Palladium-catalyzed arylation of acrylic acid by diaryliodonium salts in water

M. V. Lomonosov Moscow State University, 119899 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2685–2686, November, 1992.     

Palladium-catalyzed arylation of enynes and electron-deficient alkynes using diaryliodonium salts

A new single-pot procedure for the synthesis of aryl alkynes is described. Palladium catalyzes the coupling reaction of diaryliodonium compounds with enynes and electron-deficient alkynes to give aryl alkynes in good yields.     

Copper-catalyzed direct N-arylation of N-arylsulfonamides using diaryliodonium salts in water

An efficient copper-catalyzed N-arylation of N-arylsulfonamides with diaryliodonium salts is reported. The reaction employs diaryliodonium salts and N-arylsulfonamides in water at room temperature, giving the products in moderate to excellent yields.     

Copper-catalyzed alkene aziridination with N-tosyloxycarbamates

Pyridine copper complexes were found as active catalysts for the intramolecular aziridination of allylic N-tosyloxycarbamates and the intermolecular aziridination of styrenes with trichloroethyl N-tosyloxycarbamates. Free aziridines were easily obtained by basic deprotection of the trichloroethyl group.     

Direct arylation of arene and N-heteroarenes with diaryliodonium salts without the use of transition metal catalyst

A novel and simple transition metal-free direct arylation of arene and N-heteroarenes with diaryliodonium salts has been developed. This cross-coupling reaction is promoted only by base and gives the desired products in moderate to good yields.     

Direct arylation of tertiary amines via aryne intermediates using diaryliodonium salts

With a strategy by using diaryliodonium salts as the precursors of benzynes, direct N-arylation of tertiary amines with diaryliodonium salts was reported. Thus, the desired aromatic tertiary amines with a wide range of substituents were synthesized in moderate to excellent yields of 55–91%.     

Copper-catalyzed arylation of beta-amino alcohols

[reaction: see text] Methods for synthesizing N-aryl beta-amino alcohols and O-aryl beta-amino alcohols are described. The presence of a neighboring hydroxyl or amino group, respectively, is thought to activate beta-amino alcohols toward these transformations. These protocols significantly increase access to a variety of arylated beta-amino alcohols.     

Copper-catalyzed arylation of 1H-perfluoroalkanes

A general method has been developed for arylation of readily available 1H-perfluoroalkanes. The method employs aryl iodide and 1H-perfluoroalkane reagents, DMPU solvent, TMP(2)Zn base, and a copper chloride/phenanthroline catalyst. Preliminary mechanistic studies are reported.     

Copper-catalyzed arylation of indolin-2,3-ones with arylboronic acids

A convenient and efficient Cu(OTf)₂-catalyzed arylation of indolin-2,3-ones with arylboronic acids using cheap 1,10-phenanthroline hydrate as ligand was developed under air atmosphere, achieving 3-aryl-3-hydroxy-2-oxindoles in good to excellent yields. This catalytic system shows broad functional group tolerance. Moreover, the rigorous exclusion of air/moisture is not required in these transformations.     

Palladium-catalyzed arylation/cyclization/desulfonation cascades toward 4-aryl quinolin-2(1H)-ones with diaryliodonium salts

Palladium-catalyzed cascades of arylation/cyclization/desulfonation of ortho-aminocinnamate esters by using diaryliodonium salts afforded a wide range of 4-aryl quinolin-2(1H)-ones. As such, the desired 4-aryl quinolin-2(1H)-ones with potential biological activity has been synthesized in the yields of 34–96%.     

Palladium-catalyzed cross-coupling of diaryliodonium salts with organotin compounds

M. V. Lomonosov Moscow State University, 119899 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2683–2685, November, 1992.     

Copper-catalyzed oxidative sp3 C-H bond arylation with aryl boronic acids

An efficient method was developed for arylation of sp(3) C-H bonds using copper bromide as catalyst in absence of directing group with arylboronic acids. The oxidative arylation provides easy access to biologically active tetrahydroisoquinoline derivatives and can either use peroxide or molecular oxygen as oxidant.     

Conversion of diaryliodonium salts to aryl fluorides

The preparation of aryl fluorides by the reaction of diaryliodonium salts with KF is discussed. Generally, best results were obtained when the salt Ar₂I⁺X^? was heated with KF in the absence of solvent. The counterion, X^?, must be non-nucleophilic.