Chanlam coupling reaction of sulfamoyl azides with arylboronic acids for synthesis of unsymmetrical narylsulfamides sukyoung won, a seoeun kim, a yongju kwon, a inji shin, bc jungyeob ham d and wonsuk kim a. The chanlam reaction evanss application to diaryl ether natural product synthesis qiao, j lam, p. The reaction was facilitated in meoh in an open flask at room temperature. Copperpromoted chanlam coupling between enaminones and aryl. The discovery of the chan lam amination provided a cn bond forming process that was mild, convenient, and inexpensive, offering an alternative to complementary methods using other transition metals tms. The regioselectivityof this insertiondependson the nature of the alkene, the catalyst, and the reaction conditions employed. Antibacterial and antifungal activities were evaluated and compared. Chanlam coupling reaction of sulfamoyl azides with arylboronic. Goals of this study a major limitation of the chan lam. This reaction allows aryl carbonheteroatom bond formation via an oxidative coupling of boronic acids, stannanes or siloxanes with nh or. Herein, we attempt to trace the origin of these chemistry householdname reactions and chart their evolution. Mechanistic development and recent applications of the. Chemoselective chan lam coupling reactions between benzimidazoline2thiones and arylboronic acids. Synthesis of naryl1,2,4triazoles via chanlam coupling reaction 2.
An efficient method was developed for the synthesis of unsymmetrical narylsulfamides using sulfamoyl azides and arylboronic acids in the presence of 10 mol% of copper chloride as the catalyst. Request pdf chanlam cx coupling reaction arylation of a wide range of nhohsh substrates by oxidative crosscoupling with boronic acids in the presence of catalytic cupric acetate and. Request pdf chan lam cx coupling reaction arylation of a wide range of nhohsh substrates by oxidative cross coupling with boronic acids in the presence of catalytic cupric acetate and. Synthetic applications and methodology development of chan. The chanlam coupling reaction using cu 2 s without any ligand was very sluggish entry 12.
To evaluate the decoration of the n1position of the 21hpyrazinone scaffold applying. Acok inhibited only the reaction of 14 chart b, red line and was found to be beneficial to efficiency for the reaction using 12. In summary, cupromoted chan lam coupling reaction of enaminones with aryl boronic acids has been developed. The catalytic activity of the complex was found to be excellent for chanlam coupling reaction between aryl boronic acid and. The chanlam coupling may be conducted at room temperature in air, which gives it a certain advantage over the buchwaldhartwig cross coupling. Herein, we report effective reaction conditions for the chanevanslam amination of aryl bpin with alkyl and aryl amines. The chanlam coupling reaction starting from phenyldithiocarbamates and phenylboronic acids is reported. Subbareddy m an efficient and convenient approach for the synthesis of diaryl ethers via the onepot synthesis of and aryl boronic acids and phenols in the presence of copper acetate and 2,2bipyridine under ultrasonic irradiation. Development, mechanism and application of chanevanslam. The popularity of cross coupling reaction 3 colacot, t. Catalytic chan lam coupling using a tubeintube reactor.
Lam coupling, copper coordination complexes, homogeneous catalysis, mechanism. Graphene oxide immobilized copperii schiff base complex. Moreover, in recent years, the palladiumpromoted suzuki crosscoupling reaction has also become an effective and powerful methodology. Catalytic chanlam coupling using a tubeintube reactor to. The chan lam coupling may be conducted at room temperature in air, which gives it a certain advantage over the buchwaldhartwig cross coupling. The reaction with a stoichiometric amount of copper ii is also facilitated by oxygen, because reductive elimination from a copper iii species is faster. The discovery of the chanlam amination provided a cn bond forming process that was mild, convenient, and inexpensive, offering an alternative to complementary methods using other transition metals tms. A highly efficient heterogeneous coppercatalyzed chan lam coupling reaction of sulfonyl azides with arylboronic acids leading to narylsulfonamides. Request pdf chanlam cx coupling reaction arylation of a wide range of nhohsh substrates by oxidative crosscoupling with boronic acids. The ullmanntype reactions include coppercatalyzed nucleophilic aromatic substitution between various. A flow system to perform chanlam coupling reactions of various amines and arylboronic acids has been realised employing molecular oxygen as an oxidant for the reoxidation of the copper catalyst enabling a catalytic process. Recent advances in transitionmetalcatalyzed, directed aryl. This crosscoupling is generally performed by reacting aryl boronate derivatives with a variety of substrates involving nitrogen containing functional groups such as amines, amides, ureas, hydrazine, carbamates. The chan lam coupling reaction also known as the chan evans lam coupling is a cross coupling reaction between an aryl boronic acid and an alcohol or an amine to form the corresponding secondary aryl amines or aryl ethers, respectively.
The classic ullmann reaction is the synthesis of symmetric biaryls via coppercatalyzed coupling. Catalytic chanlam coupling using a tubeintube reactor to deliver molecular oxygen as an oxidant a flow system to perform chanlam coupling reactions of various amines and arylboronic acids has been realised employing molecular oxygen as an oxidant for the reoxidation of the copper catalyst enabling a catalytic process. The chan lam cross coupling classically allows cuiimediated aryl carbonheteroatom bond formation via an oxidative coupling of arylboronic acids, stannanes, or siloxanes with amines, alcohols, or thiols and may be conducted at room temperature in air. Application of chanlam cross coupling for the synthesis. The discovery of the copper catalyzed chanlam coupling reaction with boronic acids more than ten. The possible mechanism for the chanlam coupling between sulfamoyl azides and arylboronic acids is presented below scheme 5.
We first chose to optimize reaction conditions for the chan lam cross coupling of phenylene diamine 1 and two separate boronic acids 2a bearing orthoome and 2c bearing metanitro to afford. A rapid and efficient protocol for cn and cs cross coupling has been developed using a new square pyramidal copper complex, cudmap 4 ii. S, clark cg, saubern s, adams j, winters mp, chan dm. In fact, complex 1 is one of the most active catalyst for chanevanslam couplings and couples a large variety of nnucleophiles using an identical, simple reaction protocol, tolerating the presence of water. The chanlam crosscoupling classically allows cuiimediated aryl carbonheteroatom bond formation via an oxidative coupling of arylboronic acids, stannanes, or siloxanes with amines, alcohols, or thiols and may be conducted at room temperature in air. Expansion of the iterative crosscoupling synthesis strategy through csp3 halide cross coupling, mida boronate synthesis, and chanlam couplings by jenna audrey klubnick thesis submitted in partial fulfillment of the requirements for the degree of master of science in chemistry in the graduate college of the. Application of chanlam cross coupling for the synthesis of n. Providing comprehensive insight into the use of copper in crosscoupling reactions, coppermediated crosscoupling reactions provides a complete uptodate collection of the available reactions and catalytic systems for the formation of carbonheteroatom and carboncarbon bonds. The chanevanslam reaction is a valuable cn bond forming process. Hplc analyses after 3 and 24 h demonstrated that monoaryl derivative 3a was a major product after 3 h and its concentration decreased after 24 h as a consequence of formation of diarylated derivative 4a table 1, entry 8. Immobilization of copper ii in organicinorganic hybrid materials. Acoh inhibited the amination of both 12 and 14 chart a. This process is experimental and the keywords may be updated as the learning algorithm improves. Synthesis of heterocycles chan lam coupling reactions and their applications on the synthesis.
Chanlam coupling is one of the most popular and easy methods to perform arylation of amines narylations. Chanlamtype sarylation of thiols with boronic acids at. Recent advances in transitionmetalcatalyzed, directed. None of the common site reactions in chanevanslam couplings are observed and excess of boronic acid is not required. In recent years, a new class of transitionmetalcatalyzed crossdehydrogenative coupling reaction has been developed for the direct formation of aryl cn bonds. Chanlam coupling reaction of sulfamoyl azides with. Aug 30, 2018 chanlam coupling is one of the most popular and easy methods to perform arylation of amines narylations.
Coupling reactions with boronic acids and derivatives jennifer x. Further, the catalyst could be easily recovered quantitatively from the reaction mixture by simple filtration and reused up to five times without significant loss in the catalytic activity. Chapter2 naryl triazoles via chanlam coupling chapter 2. Dec 24, 2017 the chanlam coupling reaction starting from phenyldithiocarbamates and phenylboronic acids is reported. This essential reference covers a broad scope of coppermediated reactions, their. Coordination complexes as catalysts for chanevanslam. Chanlam coupling reaction of sulfamoyl azides with arylboronic acids for synthesis of unsymmetrical narylsulfamides sukyoung won, a seoeun kim, a yongju kwon, a inji shin,bjungyeob ham,c and wonsuk kima a department of chemistry and nanoscience, ewha womans university, seoul 03760, south korea. Various substituted n aryl enaminones were synthesized in moderate to high yields with a good functional group tolerance. Although r1 and r2 are typically electronrich substituents, the incorporation of the iridiumiii photoredox catalyst facilitates an expanded substrate scope with aryl coupling partners. Information from its description page there is shown below. Graphene oxide immobilized copperii schiff base complex go. We report an investigation of the chan lam amination reaction. Ullmanntype reactions proceed through a catalytic cycle, and in one mechanism the copper is postulated to undergo oxidation to cu iii. Chapter 2 synthesis of naryl1,2,4triazoles via chanlam coupling.
The intermediate monohalide monostannane cyclises under the reaction conditions to yield the desired product. Over the past 20 years, this reaction has seen considerable development in its scope of. As some cu iii salts have been prepared, the suggestion for the mechanism is intriguing see also chan lam coupling. Coppercatalyzed chanlam cyclopropylation of phenols and. Chanlam crosscoupling reaction based on the cu2stmeda. Several modifications of the chanlam reaction have been reported, expanding its scope and it has since been used to synthesise several biologically active compounds 1112. This novel method provides an efficient access to n aryl enaminones. Physical chemistry inorganic chemistry organic chemistry pharmaceutical company coupling reaction these keywords were added by machine and not by the authors.
Apr 06, 2018 the reaction proceeded with good to high yields over a large variety of copperii species. A list of well known not comprehensive cc and c x bond forming reactions is given below mozorikiheck stille suzukimiyaura sonogashira buchwaldhartwig chanlam. Unlike the coupling of sulfamides and bo editors collection. This file is licensed under the creative commons attributionshare alike 4. A combination of spectroscopy, computational modeling, and crystallography has identified the structures of key intermediates and allowed a complete mechanistic description to be presented, including offcycle inhibitory processes, the source of amine and organoboron reactivity issues, and the origin of competing oxidation. These reactions were subsequently shown to work with a large number of nucleophiles and tolerated a variety of substrates, making the process one of the most efficient ways for cno coupling 11. Recent advances in transitionmetalcatalyzed, directed aryl chnh crosscoupling reactions martyn c. Here we report a spectroscopic investigation of the chanlam amination reaction, providing a complete mechanistic description.
Catalytic chan lam coupling using a tubeintube reactor to. Chans and became interested because of the importance of novel. The chanlam coupling is catalyzed by copper complexes. The stillekelly coupling is a palladium catalysed intramolecular cross coupling using distannanes such as hexabutyldistannane or hexamethyldistannane. Jan 31, 2019 over the last two decades, nheterocyclic carbene nhccopper catalysts have received considerable attention in organic synthesis. Chanlam cross coupling allowed efficient synthesis of n,ndisubstituted orthophenylene diamines bearing strong electron donating or withdrawing groups, such as nitro or methoxy groups, with. Effect of addition of a acoh, b acok, and c pinacol to the chanlam amination of 11a with 12 blue line and 14 red line under standard conditions. The chan lam coupling is catalyzed by copper complexes.
Over the last two decades, nheterocyclic carbene nhccopper catalysts have received considerable attention in organic synthesis. The chanlamevans coupling has recently emerged as an interesting alternative to the more classical copper. Chanevanslam amination of boronic acid pinacol bpin. Over the past 20 years, this reaction has seen considerable. Density functional theorysupported studies of structural. However, aryl boronic acid pinacol bpin ester reagents can be difficult coupling partners that often deliver low yields, in particular in reactions with aryl amines. The catalytic activity of the complex was explored in chan. The structures of new compounds were confirmed by ir and.
The catalytic activity of the complex was found to be excellent for chanlam coupling reaction between aryl boronic acid and amine, amide, azide or thiol. Catalytic chanlam coupling using a tubeintube reactor. A tubeintube gas reactor has been used to simplify the delivery of the oxygen accelerating the optimisation phase and allowing easy access to. Copperiipromoted oxidative aryl transfer from arylboron derivatives, 115 4. Toward green, cheap and environmentally friendly catalysis chun ho lam 2nd november, 2011 1. Density functional theorysupported studies of structural and. Lam coupling reaction of amines and arylboronic acids without using any co. Mechanistic development and recent applications of the chan.
The chanlam coupling reaction also known as the chanevanslam coupling is a crosscoupling reaction between an aryl boronic acid and an alcohol or an amine to form the corresponding secondary aryl amines or aryl ethers, respectively. Coppercatalyzed chanlam coupling between sulfonyl azides. The chan lam coupling reaction using cu 2 s without any ligand was very sluggish entry 12. This article summarizes the synthetic applications of this reaction and. N bond forming chanlam coupling reaction showing conditions from the kobayashi and lab. In summary, cupromoted chanlam coupling reaction of enaminones with aryl boronic acids has been developed. Transition metalmediated formation of cn bonds is an essential synthetic methodology.
Unlimited viewing of the articlechapter pdf and any associated supplements and figures. The narylation of various heterocycles is now a powerful new synthetic tool. Despite the popularity of copper complexes containing monodentate nhc ligands and recent development of polynhc platforms, their application in cc and cheteroatom crosscoupling reactions has been limited. Herein, we report effective reaction conditions for the chan evans lam amination of aryl bpin with alkyl and aryl amines. The reaction could be carried out in the presence of only 2 mol% of the copper catalyst in methanol at room temperature within a short time. The journal of organic chemistry 2019, 84 18, 1152411532. The chanlam coupling reaction also known as the chanevanslam coupling is a.
Mechanism of the chanlam coupling organic chemistry portal. Various substituted naryl enaminones were synthesized in moderate to high yields with a good functional group tolerance. Henry left was born in 1993 in livingston, scotland. Notably, copperii formate cuhco 2 2, a copperii species that is seldom used in chanlam coupling was found to be nearly as effective as the optimal catalyst, cuoac 2. Professor evans group found out about the discovery of coppermediated oarylation reaction on a national organic symposium poster of dr. Analysis of the mechanism is complicated by the lability of copper reagents and the multicomponent nature of the reaction. Jul 23, 2015 chanlam cross coupling allowed efficient synthesis of n,ndisubstituted orthophenylene diamines bearing strong electron donating or withdrawing groups, such as nitro or methoxy groups, with. The complex was successfully synthesized via a disproportionation reaction of cui and dmap in dmso. The chan evans lam reaction is a valuable cn bond forming process. Chan lam coupling reaction of sulfamoyl azides with arylboronic acids for synthesis of unsymmetrical narylsulfamides sukyoung won, a seoeun kim, a yongju kwon, a inji shin,bjungyeob ham,c and wonsuk kima a department of chemistry and nanoscience, ewha womans university, seoul 03760, south korea. This novel method provides an efficient access to naryl enaminones. The reaction proceeded with good to high yields over a large variety of copperii species. Copperpromoted chanlam coupling between enaminones and. Several modifications of the chanlam reaction have.
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