Transition metalcatalyzed decarboxylative cross coupling reactions have recently emerged as a new and important category of organic transformations that find versatile applications in the construction of carboncarbon and carbonheteroatom bonds. Nmp is a wellknown solvent for suzuki reactions 12 and also a good solvent for 4. Nov 17, 2017 citu, now commercially available, 11 is an inexpensive, dualpurpose reagent that enables both solid and solutionphase acylation and decarboxylative cross coupling reactions. Pdcatalyzed decarboxylative benzylic coupling of nitrogencontaining heteroaromatics with allyl electrophiles allylationaza cope rearrangement did not translate to more general benzylic couplings new method for the decarboxylative coupling of nitrobenzene acetic esters n o o bn pd oxidative addition ph n bn pd ph n bn pd ph h. Methyl, primary, and secondary alkyl groups can all be coupled in good yield 77%. Recent developments in decarboxylative cross coupling reactions between carboxylic acids and nh compounds sattar arshadi,a saeideh ebrahimiasl,bc akram hosseinian, d aazam monfareda and esmail vessally a carboxylic acids and their derivatives are ubiquitous. Mar 06, 2015 decarboxylative crosscouplings are an attractive strategy for the construction of biaryl bonds because they constitute a greener and more economical alternative to traditional cross coupling reactions. A novel methodology for the decarboxylative suzukimiyauratype coupling has been established. A new method for the decarboxylative coupling of alkyl nhydroxyphthalimide esters nhp esters with aryl iodides is presented. For this purpose, a general procedure for all three reaction types suzuki, heck and sonogashira was developed. Catalyzed decarboxylative suzuki and heck couplings of azaindole. The methodology is compatible for performing decarboxylative halogenation followed by decarboxylative suzuki. Jul 11, 2012 recently we reported pdcatalyzed decarboxylative crosscoupling of cyanoacetate salts with aryl halides and triflates. As shown in table 2, both electronde cient and electronrich aryl iodides 1b1j underwent the decarboxylative crosscoupling reaction with c 6f 5cook smoothly to a.
Decarboxylative alkylaryl cross couplings via nickel catalysis with redoxactive esters. The reaction is useful for synthesis of polyfluorobiaryls from readily accessible and nonvolatile polyfluorobenzoate salts. Suzuki cross coupling reaction is one of the most famous reaction in the field of chemistry. Palladiumcatalyzed asymmetric suzukimiyaura coupling reaction is a useful method for the synthesis of axially chiral biaryl compounds 50. This method was used to synthesize a diverse set of alkyl aryl ethers using readily available alkyl carboxylic acids, including many natural products. Pdf the beginning of the 21st century has seen tremendous growth in the field of decarboxylative activation.
Preparative scale decarboxylative crosscoupling reactions. The suzukimiyaura coupling of nitroarenes journal of. This reaction shows good functional group tolerance and is useful for the synthesis of. Amino acids via the merger of photoredox and nickel catalysis j. Wenjun zhao department of chemistry michigan state university nov. These methods have profoundly changed the protocols for the construction of natural products, building blocks for supramolecular chemistry and selfassembly, organic materials and polymers, and lead. Decarboxylative coupling by photoredox and chiral nickel catalysis significance. Co2 r1 o hm r2x r1r2 o intramolecular couplings intermolecular couplings. It is best suited for practitioners seeking a safe alternative to the standard array of coupling reagents, particularly on large scale.
Decarboxylative csp3heteroatom coupling of alkyl nhpi esters has been achieved using tandem photoredox and copper catalysis. Synthesis of biaryls via catalytic decarboxylative coupling. Nicatalyzed electrochemical decarboxylative cc couplings. The stateoftheart process for biaryl synthesis from ubiquitous carboxylic acids is decarboxylative cross coupling involving loss of carbon dioxide co 2. Advances in decarboxylative cross coupling for biaryl synthesis. Synthesis of biaryls via decarbonylative palladiumcatalyzed. In recent years, decarboxylative and desulfitative cross. In addition, a few examples of allylation have been reported in the intermolecular decarboxylative coupling even though allyl alkynes are important building blocks. Toward green, cheap and environmentally friendly catalysis chun ho lam 2nd november, 2011 1.
It is widely used to synthesize polyolefins, styrenes, and substituted biphenyls. The thesis details the development of a decarboxylative synthesis of aryl ethers using a relatively new iron catalyst and a novel decarboxylative coupling of coumarins catalyzed by palladium. Benzoic acids are now recognised as atomeconomic alternatives to traditional cross coupling partners and they also benefit from being cheap, readilyavailable and shelfstable reagents. Coppercatalyzed decarboxylative cn crosscoupling for n. Si1 coppercatalyzed decarboxylative cn cross coupling for narylation yun zhang, sejal patel, nello mainolfi, novartis institutes for biomedical research inc. Synthesis of biaryls via decarbonylative palladium. Transition metalcatalyzed decarboxylative cross coupling reactions have recently emerged as a new and important category of organic transformations that find versatile applications in the. In contrast to traditional crosscouplings, which require the prior preparation of organometallic reagents, we use a copper catalyst to generate the carbon nucleophiles in situ, via decarboxylation of easily. Protodecarboxylation operates in the case of azaindole. Pdcatalyzed decarboxylative cross coupling of potassium polyfluorobenzoates with aryl bromides, chlorides, and triflates is achieved by using diglyme as the solvent. Suzukimiyaura coupling an overview sciencedirect topics.
This process uses iodine or a bromine source as both the decarboxylation mediator and the terminal oxidant, thus avoiding the need for stoichiometric amounts of transition metal salts previously required. Nickelcatalyzed deformylative suzuki miyaura cross coupling and related dft studies on the role of trifluoroacetophenone. Recent advances in decarboxylative and desulfitative cross. Decarbonylative organoboron crosscoupling of esters by nickel catalysis kei muto1, junichiro yamaguchi1, djamaladdin g. Finally, the same concept can be applied to the sp 2. Recently we reported pdcatalyzed decarboxylative cross coupling of cyanoacetate salts with aryl halides and triflates. Phil baran running a nickelcatalyzed decarboxylative alkylalkyl cross coupling. Decarboxylative borylation could also convert raes, which are electrophiles in cross couplings, into bpin esters that serve as nucleophiles in suzuki reactions e. Pdf advances in decarboxylative cross coupling for.
Mechanistic studies have revealed that the catalytic cycle of this reaction is initiated by the cleavage of the arylnitro arno2 bond by palladium, which represents an unprecedented elemental reaction. Suzuki coupling the scheme above shows the first published suzuki coupling, which is the palladiumcatalysed cross coupling between organoboronic acid and halides. Suzuki reaction the problem in cross couplings is the synthesis of the carbon nucleophiles alternative direct arylations are regioselective not for all arenes regiospecific decarboxylative coupling of carboxylates generation of organometallic reagents from simple metal carboxylates. I cli i ome ome l cl cl cl cl ome meo quinoline, 220 uc coperbnz.
Palladiumcatalyzed decarboxylative spsp coupling of. Organic seminar recent advances in ni catalyzed suzuki coupling. In contrast to traditional cross couplings, which require the prior preparation of organometallic reagents, we use a copper catalyst to generate the carbon nucleophiles in situ, via decarboxylation of easily. In 1966, nilsson reported the first decarboxylative ullmann reaction. A novel methodology for the decarboxylative suzuki miyauratype coupling has been established. The unique properties of ni catalysts facilitate the activation of traditionally inert substrates, tolerate alkyl coupling partners that undergo decomposition via. Synthesis of biaryls via the suzukimiyaura coupling smc reaction using nitroarenes as an electrophilic coupling partners is described. Aug 27, 2018 reported here is a tandem photoredox and copper catalysis to achieve decarboxylative csp 3. Theoretical analysis of factors controlling pdcatalyzed decarboxylative coupling of carboxylic acids with olefins. We present a safe and convenient cross coupling strategy for the largescale synthesis of biaryls, commercially important structures often found in biologically active molecules.
Decarboxylativedecarbonylative couplings of heteroaryl. Decarboxylative suzukimiyaura coupling of heteroaromatic. H elimination with pd, and enable stereoconvergent cross. Several conjugated oligomers were synthesized in high yields using various aryl bromides. Apr 29, 2019 nickelcatalyzed deformylative suzukimiyaura cross coupling and related dft studies on the role of trifluoroacetophenone. Apr 01, 2017 synthetic efforts towards the total synthesis of the natural product drimentine c are described. Suzuki and miyaura3,4 postulated that activation of the boron using a negatively. The first example of a decarboxylative crosscoupling reaction. Introduction of decarboxylative coupling reactions different types of decarboxylative coupling reactions applications in organic synthesis i. The use of relatively cheap and stable carboxylic acids to replace organometallic reagents enables the decarboxylative cross coupling reactions to. Unlike the cucatalyzed decarboxylation cross coupling where oxidative addition is the ratelimiting step. Theoretical analysis of factors controlling pdcatalyzed.
The development of metalcatalyzed cross coupling reactions over the past 30 years has revolutionized the way, carboncarbon bonds between sp and sp 2 carbon atoms are formed. C bondforming reactions to the coupling of aromatics with sp 3hybridized electrophiles. The reaction conditions employed displayed relatively low sensitivity toward the presence of water. The advancement of palladiumcatalyzed decarboxylative. Phil baran running a nickelcatalyzed decarboxylative. Ironcatalyzed decarboxylative cross coupling reactions and palladium. This represents the first extension of decarboxylative c. Nalkylanilines via decarboxylative couplings substituted anilines1,2 are ubiquitous in pharmaceuticals3 and material science. This coupling method allows for rapid transformation of readily available alkyl carboxylic acids into alkyl aryl amines, primary amines or alkyl aryl ethers, which are important compounds in medicinal chemistry. To elucidate the mechanism for this reaction, we now carry out a density functional theory study on the cross coupling of potassium cyanoacetate with bromobenzene. We hoped that the spectroscopic analysis of the behavior of such novel. To elucidate the mechanism for this reaction, we now carry out a density functional theory study on the crosscoupling of potassium cyanoacetate with bromobenzene. Recent developments in decarboxylative crosscoupling. Csp2 bondforming transformation exhibits excellent substrate generality and functional group compatibility.
An operationally simple continuousflow version of this transformation using a commercial electrochemical flow reactor represents a robust and scalable synthesis of value added coupling process. Preprint title decarboxylative bromination of thiazole core and consecutive cross coupling reactions. Nicatalyzed electrochemical decarboxylative cc couplings in. Oct 12, 2011 transition metalcatalyzed decarboxylative cross coupling reactions have recently emerged as a new and important category of organic transformations that find versatile applications in the construction of carboncarbon and carbonheteroatom bonds. Figure 14 the suzuki miyaura reaction 1979 10 figure 15 generic palladiumcatalyzed cross coupling. The suzuki miyaura cross coupling is a metalcatalysed reaction in which boronbased nucleophiles and halidebased electrophiles are reacted to form a single molecule. Pdcatalyzed decarboxylative cross coupling of potassium. An effective decarboxylative cross coupling involving a 3,4dioxypyrrole is reported. Aryl allyl carbonates underwent facile decarboxylative coupling in presence of a new iron catalyst. Nickelcatalyzed decarboxylative coupling reaction of. This umpolung approach is particularly strategic in the case of 36e, as 2pyridylboronic acid or organozinc species are often not viable suzuki. No copper salt or other transmetalating agent was required. However, the scope of these methods is severely limited, mainly due to specific substitution. Ironcatalyzed decarboxylative cross coupling reactions and.
If you wish to distribute this article to others, you can order highquality copies for your following the guidelines here. Suzuki miyaura coupling or suzuki coupling is a metal catalyzed reaction, typically with pd, between an alkenyl vinyl, aryl, or alkynyl organoborane boronic acid or boronic ester, or special cases with aryl trifluoroborane and halide or triflate under basic conditions. We now were curious to investigate cross coupling behaviour of the 5bromothiazoles. The biaryl motif is a building block in many drugs, agrochemicals, and materials, and as such it is highly desirable as a synthesis target. The scope of this decarboxylative suzuki reaction has been greatly diversified. Mechanism of palladiumcatalyzed decarboxylative cross. While citu is not recommended for use in the previously disclosed decarboxylative suzuki cross coupling reaction, 7 it can be readily employed for the analogous nicatalyzed negishi alkylation, arylation, alkenylation, and alkynylation reactions, as well as for solution. The chiral palladiumphosphine complexes are probably the most oftenused catalysts. Transition metal catalyzed decarboxylative crosscoupling.
Heck, eiichi hegishi, and akira suzuki for palladiumcatalyzed cross couplings in organic synthesis negishi suzuki heck kumada d. Nov 01, 2017 vapourtec rseries has been used to achieve rapid reaction times and high conversion of a suzuki coupling, using a commercially available supported palladium catalyst. Advances in nickelcatalyzed crosscoupling reactions have expanded the chemical space of accessible structures and enabled new synthetic disconnections. Reported here is a tandem photoredox and copper catalysis to achieve decarboxylative csp 3. A thorough analysis of this topic will cover reactivity trends in transition metal catalysed decarboxylations and the current state of decarboxylative cross couplings for biaryl synthesis. It is a very effective method for making carbon carbon bonds. An electrochemically driven, nickelcatalyzed reductive coupling of nhydroxyphthalimide esters with aryl halides is reported. Three distinct approaches are discussed incorporating palladium. Decarbonylative organoboron crosscoupling of esters by. In contrast to previous studies that form alkyl radicals from carboxylic acid derivatives, no photocatalyst, light, or arylmetal reagent is needed, only nickel and a reducing agent zn. This decarboxylative csp3csp2 bondforming transformation exhibits excellent substrate generality and functional group compatibility.
Recent advances in decarboxylative couplings reported by lucas hernandez 10252016 introduction decarboxylation reactions stem back to the kolbe electrolysis in 1849, where carboxylic acids and carboxylate salts were homocoupled. Nickelcatalyzed suzukimiyaura crosscouplings of aldehydes. Scale up of the decarboxylative cross coupling reaction recently, we have presented a safe and convenient cross coupling strategy for the large scale synthesis of biaryls. The reaction proceeds under mild conditions in a divided electrochemical cell and employs a tertiary amine as the reductant. Catalyzed decarboxylative suzuki and heck couplings. Pdf recent progress in decarboxylative oxidative cross. Decarboxylative cross coupling reactions are chemical reactions in which a carboxylic acid is reacted with an organic halide to form a new carboncarbon bond, concomitant with loss of co 2. In 1958, nilsson reported his findings regarding an ullmann coupling. Attempts by negishi1,2 to crosscouple organoboron reagents with organic halides failed because the neutral threecoordinate boron species were not nucleophilic enough to efficiently transmetalate. Decarbonylative organoboron cross coupling of esters by nickel catalysis kei muto1, junichiro yamaguchi1, djamaladdin g.
Transitionmetalfree decarboxylative coupling reactions for the synthesis of propargyl alcohols asian j. The wide diversity of useful reactivity that is exclusive to boronic acids, such as cross coupling, oxidation, amination, and homologation, will open distinct possibilities in retrosynthetic analysis. The use of relatively cheap and stable carboxylic acids to replace organometallic reagents enables the decarboxylative cross coupling. Decarboxylative crosscoupling ntj princeton university. Cross coupling reactions 2010 nobel prize in chemistry awarded jointly to richard f. Decarboxylative bromination of thiazole core and consecutive. The transitionmetal catalyzed carbonhydrogen bond activation and functionalization reaction is one of the versatile methods to construct the carboncarbon bond in organic synthesis, which has become a hot topic in current organic chemistry and has been widely used in the synthesis of natural products and pharmaceutical intermediates.
Mechanisms of nickelcatalyzed crosscoupling reactions. Typically, only orthosubstituted or electronically biased benzoic acids are suitable substrates for decarboxylative suzuki cross coupling, whereas the present method could be employed for any functionalized position on the benzene ring of carboxylic acids as well as for electrondonating, electronneutral, or electronwithdrawing carboxylic. Ironcatalyzed decarboxylative cross coupling reactions. Jun 29, 2015 the suzukimiyaura crosscoupling is a metalcatalysed reaction in which boronbased nucleophiles and halidebased electrophiles are reacted to form a single molecule. Suzuki reaction the problem in crosscouplings is the synthesis of the carbon nucleophiles alternative direct arylations are regioselective not for all arenes regiospecific decarboxylative coupling of carboxylates generation of organometallic reagents from simple metal carboxylates. This work may also accelerate the discovery and development of new boroncontaining therapeutics. In many publications this reaction also goes by the name suzukimiyaura reaction and is also referred to as the suzuki coupling. C sp2bearing carboxylates the carboxyl moiety most commonly found in biomass might be rendered suitable for decarboxylative aryl couplings via the use of a novel. Transition metalcatalyzed decarboxylative crosscoupling.
1324 1442 932 1036 1508 352 1622 530 1303 1568 1417 285 1331 549 96 470 1151 170 1595 1255 194 687 1140 1181 402 998 46