CuI/Oxalic Diamide Catalyzed Coupling Reaction of (Hetero)Aryl Chlorides and Amines

Zhou, Wei; Fan, Mengyang; Yin, Jun; Jiang, Yongwen; Ma, Dawei

doi:10.1021/jacs.5b08411

Cited by 228 publications

(93 citation statements)

References 64 publications

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“…The use of oxalamides L2 – L4 , which are derived from 2‐phenoxy‐ or 2‐phenyl‐substituted anilines, gave better results, but incomplete conversion was still observed (entries 2–4). To our surprise, improved conversion was observed when N‐aryl‐N′‐alkyl‐substituted oxalamide L5 was used as the ligand (entry 5), which was inconsistent with the trends observed in our previous studies on aryl amination …”

Section: Cui Catalyzed Coupling Of 4‐chlorotoluene With Phenol In Thecontrasting

confidence: 98%

CuI/Oxalamide Catalyzed Couplings of (Hetero)aryl Chlorides and Phenols for Diaryl Ether Formation

et al. 2016

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Couplings between (hetero)aryl chlorides and phenols can be effectively promoted by CuI in combination with an N‐aryl‐N′‐alkyl‐substituted oxalamide ligand to proceed smoothly at 120 °C. For this process, N‐aryl‐N′‐alkyl‐substituted oxalamides are more effective ligands than bis(N‐aryl)‐substituted oxalamides. A wide range of electron‐rich and electron‐poor aryl and heteroaryl chlorides gave the corresponding coupling products in good yields. Satisfactory conversions were achieved with electron‐rich phenols as well as a limited range of electron‐poor phenols. Catalyst and ligand loadings as low as 1.5 mol % are sufficient for the scaled‐up variants of some of these reactions.

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Section: Cui Catalyzed Coupling Of 4‐chlorotoluene With Phenol In Thecontrasting

confidence: 98%

CuI/Oxalamide Catalyzed Couplings of (Hetero)aryl Chlorides and Phenols for Diaryl Ether Formation

et al. 2016

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“…The desired product could be obtained when the coupling was carried out in DMSO at 120 °C, but yield was only 30% because of poor conversion (entry 1). Two other diaryl‐substituted oxalamide ligands L2 and L3 that performed well for coupling with amines,, gave similar results (entries 2 and 3). Interestingly, modifying the aryl moiety of oxalic diamide ligands with the furfurylamine framework led to the discovery of BFMO ( L4 ) as an excellent ligand (entry 4).…”

Section: Cu2o‐catalyzed Coupling Of 4‐bromoanisole With Indole Under mentioning

confidence: 62%

Copper(I) Oxide/N,N′‐Bis[(2‐furyl)methyl]oxalamide‐Catalyzed Coupling of (Hetero)aryl Halides and Nitrogen Heterocycles at Low Catalytic Loading

Pawar

et al. 2017

Adv Synth Catal

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An easily preparedo xalic diamide is ap owerful ligandf or the copper-catalyzed coupling of aryl halides with nitrogen heterocycles.O nly 1-2mol% each of copper(I) oxide and N,N'-bis[(2-furyl)methyl]oxalamide (BFMO) are needed to form N-arylation productsu nder mild conditions.M ore than 10 different typeso fn itrogen heterocycles are compatible with these conditions,t hereby givingt he corresponding N-arylation products.

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“…Various ligands were then screened in order to increase the yield (Supplementary Table 1), and 2,2,6,6-tetramethyl-3,5-heptanedione (L1, 30 mol%) was the best among the first set of 20 ligands, giving 3a in 58% yield (Table 1, entry 2). Recently, a modular ligand system was developed based on oxoacetic acids and oxalamides for copper-catalysed amination of aryl chlorides 42,43 . When oxalamides were used for our reaction, the yields were modest, probably due to poor solubility (Supplementary Table 1) However, when 2-(2,6-dimethylphenylamino)-2-oxoacetic acid (L2) was used, the yield was significantly improved to 71% (Table 1, entry 3).…”

Section: Nature Catalysismentioning

confidence: 99%

Decarboxylative C(sp3)–N cross-coupling via synergetic photoredox and copper catalysis

et al. 2018

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A mines are one of the most important structural motifs in pharmaceuticals, agrochemicals and organic materials 1,2 . Alkylation and reductive amination reactions are still commonly used to prepare and modify amines, and new methods derived from reductive amination, such as the borrowing hydrogen 3 strategy, have been reported [4][5][6][7] . Nevertheless, the most significant development in amine synthesis has been transition-metal-catalysed C-N coupling of aryl electrophiles (halides and pseudo halides) with amine nucleophiles [8][9][10][11] (Fig. 1a). The C-N coupling of alkyl electrophiles, however, is largely under-developed (Fig. 1a). A perceived difficulty is β -hydrogen elimination from a metal alkyl intermediate originated from oxidative addition of the alkyl electrophile, which has posed considerable challenges in analogous C-C crosscoupling of alkyl electrophiles [12][13][14] . Moreover, the product-yielding C(sp 3 )-N reductive elimination step is rarely demonstrated 15 . A notable exception is the light-induced, copper-catalysed C-N coupling of alkyl halides recently developed [16][17][18] . Nevertheless, the scope of amine nucleophiles is limited to carbazoles 16,18 and amides 17,19 . Alternative, formal C-N coupling of alkyl electrophiles via the addition of alkyl radicals to nitroarenes has been reported 20,21 .The group of Baran has recently trailblazed the use of redox-active esters derived from alkyl carboxylic acids as superior surrogates of alkyl halides in decarboxylative C-C cross-coupling reactions [22][23][24] . Extension to a decarboxylative carbon-heteroatom, particularly C-B bond formation has also been reported 19,[25][26][27][28][29] . The key attributes of alkyl carboxylic acids 30,31 are their unparalleled availability, stability and non-toxic nature, which are in stark contrast with alkyl halides, ketones and aldehydes. While several precedents of decarboxylative imidation 32 and amination 19,33 are known, they are limited to a narrow scope of very special substrates or intramolecular reactions. A general metal-catalysed decarboxylative C-N coupling of redox-active esters with anilines will provide valuable methodology for the synthesis of alkylated anilines (Fig. 1b), which requires alkyl halides and carbonyl compounds 6 as starting reagents using the currently standard methods of alkylation and reductive amination, respectively. Further foreseen advantages of such a decarboxylative amination include applicability to bulky primary and secondary alkyl groups and immunity to over-alkylation, both of which are major limitations of direct alkylation (Fig. 1b). Despite its conceptual simplicity and resemblance to decarboxylative C-C coupling, the intermolecular decarboxylative C-N coupling of redoxactive esters poses significant hurdles. The activation principle of redox-active esters originates from amide-bond synthesis; thus, amide formation can compete when amine nucleophiles are used. Moreover, decarboxylative C-C coupling reactions of redox-active esters were, until now, all init...

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CuI/Oxalic Diamide Catalyzed Coupling Reaction of (Hetero)Aryl Chlorides and Amines

Cited by 228 publications

References 64 publications

CuI/Oxalamide Catalyzed Couplings of (Hetero)aryl Chlorides and Phenols for Diaryl Ether Formation

CuI/Oxalamide Catalyzed Couplings of (Hetero)aryl Chlorides and Phenols for Diaryl Ether Formation

Copper(I) Oxide/N,N′‐Bis[(2‐furyl)methyl]oxalamide‐Catalyzed Coupling of (Hetero)aryl Halides and Nitrogen Heterocycles at Low Catalytic Loading

Decarboxylative C(sp3)–N cross-coupling via synergetic photoredox and copper catalysis

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