Asymmetric suzukimiyaura coupling of heterocycles via. Pdf fast suzukimiyaura crosscoupling reaction with. It is a very effective method for making carbon carbon bonds. Substituents such as benzyl, phenyl, allyl, and alkyl are tolerated at the 1. The suzukimiyaura crosscoupling as a versatile tool for. Aphos palladium complexes for efficient suzuki coupling. Miyaura cross coupling reactions of aryl and heteroaryl chlorides with potassium aryl and heteroaryltrifluoroborates have been accomplished with the supporting ligand s phos in good to excellent yield. Wellelaborated methods allow the preparation of different products from all of the combinations of halides and stannanes depicted below.
Suzukimiyaura crosscoupling reaction catalyzed by a highly. Recent catalyst and methods developments have broadened the possible applications enormously, so that the scope of the reaction partners is not restricted to aryls, but includes alkyls, alkenyls and. The suzuki cross coupling reaction is the organic reaction of an organohalide with an organoborane to give the coupled product using a palladium catalyst and base. Metal catalyzed suzukimiyaura crosscoupling preprints. Design and synthesis of phosphine ligands for pallaiumcatalyzed coupling reactions by william scott brown. A highly efficient precatalytic system xphospdg2 for the suzukimiyaura crosscoupling of 7chloro1hpyrrolo2,3cpyridine employing low catalyst loading. Facilitating roomtemperature suzuki coupling reaction. Nov 24, 2006 suzuki miyaura cross coupling has become a powerful synthetic tool for the synthesis of carboncarbon bonds, 1 and recent advances have expanded the scope of this coupling to include alkyl halide cross coupling. Sterically demanding arylalkyl suzukimiyaura coupling. The mechanism begins with oxidative addition of the organohalide to the pd0 to form a pdii complex.
Facilitating roomtemperature suzuki coupling reaction with. Palladium catalysts for the suzuki crosscoupling reaction. Miyaura crosscoupling reactions of aryl and heteroaryl chlorides with potassium aryl and heteroaryltrifluoroborates have been accomplished with the supporting ligand sphos in good to excellent yield. Palladiumcatalyzed suzukimiyaura crosscoupling reactions. Suzuki and miyaura3,4 postulated that activation of the boron using a negatively. It was first published in 1979 by akira suzuki and he shared the 2010 nobel prize in chemistry with richard f. A large variety of palladium suzukimiyaura crosscoupling reactions. The suzuki reaction is an important type of coupling reaction, a designation that encompasses a variety of processes that combine or couple two hydrocarbon fragments with the aid of a catalyst in the suzuki reaction, palladium in a basic environment.
As suzuki miyaura coupling is the most widely used method for cc bond forming heteroaryl elaboration 19, the ability to use heterocycles is. We thus envisioned that antphos would be advantageous for sterically demanding arylalkyl suzukimiyaura coupling and further broaden the synthetic utility of suzukimiyaura coupling. Xphos pd g2 is a secondgeneration buchwald catalyst typically used for palladiumcatalyzed suzuki miyaura cross coupling reactions. In this paper, lbphoshbf4 salt has been applied for the pdcatalysed suzuki coupling reactions of optically active z. Phos hbf 4 was used in the suzuki coupling reaction of 2. A highly enantioselective palladiumwj phos catalyzed suzuki miyaura coupling reaction for efficient construction of axially chiral biaryl monophosphine oxides was developed. The pdcatalyzed suzukimiyaura reaction has found widespread use in the. Reactions of aryl chlorides with aryl boronic acids generally require heating for extended periods. The complex proved to be a highly stable and efficient catalyst for substrates with a wide range of functional groups in suzuki miyaura cross coupling reactions under air at room temperature. Cross coupling reactions 2010 nobel prize in chemistry awarded jointly to richard f. It is a powerful crosscoupling method that allows for the synthesis of conjugated olefins, styrenes, and biphenyls. Organic seminar recent advances in ni catalyzed suzuki coupling. Heck, eiichi hegishi, and akira suzuki for palladiumcatalyzed cross couplings in organic synthesis negishi suzuki heck kumada d. The scheme above shows the first published suzuki coupling, which is the palladiumcatalysed cross coupling between organoboronic acid and halides.
A phos introduction the suzuki miyaura cross coupling reaction of heteroaryl halides is of particular interest to the pharmaceutical industry since many biologically active compounds are accessed through this methodology. A series of axially chiral biaryl monophosphine oxides were obtained in good yields and with high enantioselectivities. Its palladium complexes exhibit high activity for suzuki coupling reactions involving aryl chlorides, which are unreactive with palladium complexes of most other phosphine ligands. Review on green chemistry suzuki cross coupling in aqueous media robert franzen and youjun xu abstract. Grignard reagent negishi coupling hiyama coupling suzuki coupling kumada coupling 1. The suzuki crosscoupling reaction is a very efficient, reliable, and environmentally friendly method for the introduction of novel carboncarbon bonds into molecules. A new pdp phos cl 2 complex was synthesized and characterized by 1 h nmr, c nmr, 31 p nmr, and xray single crystal structure determination. The development of new means of activating molecules and bonds over old catalysts for cc bond. Axially chiral biaryl monophosphine oxides enabled by. The catalyst system with this new ligand was found to be highly effective in facilitating the reaction even at catalyst loading levels in the parts per million range e. Lowary department of chemistry, the ohio state university 100 west 18th avenue, columbus, ohio 43210 notes for the student in the following document, notes preceded by ins are notes for the instructor and can be. American elements can produce most materials in high purity and ultra high purity up to 99. The suzuki reaction is an organic reaction, classified as a cross coupling reaction, where the coupling partners are a boronic acid and an organohalide catalyzed by a palladium 0 complex.
An easy way for cc bonding nobel lecture, december 8, 2010 by akira suzuki hokkaido university, sapporo, hokkaido, japan. Pdf palladiumcatalyzed suzukimiyaura crosscoupling in. Phoshbf 4 was used in the suzuki coupling reaction of 2. Aryl, vinyl, alkyl and heteroaromatic boronic acids may be coupled with optically active. Myers the suzuki reaction chem 115 harvard university.
A highly efficient precatalytic system xphospdg2 for the. The suzuki coupling reaction is one of the most practiced classes of catalytic cc bond formation. Fast suzukimiyaura crosscoupling reaction with hexacationic triarylphosphine bndendriphos as ligand. Homogeneously catalysed suzuki coupling reaction depositonce.
The impact of the suzuki miyaura reaction smc on academic and industrial research as well as on production has been immense. 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. Among many synthetic applications of suzuki coupling reac. Suzuki coupling the stille coupling is a versatile cc bond forming reaction between stannanes and halides or pseudohalides, with very few limitations on the rgroups. Therefore, the water soluble ligand sphos developed by buchwald was. 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. Suzukimiyaura crosscoupling reactions of benzyl halides. Pdf carboncarbon crosscoupling reactions are among the most important processes in. Miyaura couplings of a 3pyridyl boronbased nucleophile with. The development of new means of activating molecules and. Qphos are highly successful for both electronpoor and electronrich aryl bromides and chlorides table 3. The practicability of this reaction was validated in the straightforward synthesis of axially. The suzuki miyaura reaction smr, involving the coupling of an organoboron reagent and an organic halide or pseudohalide in the presence of a palladium or nickel catalyst and a base, has arguably become one of most utilized tools for the construction of a cc bond. Akira suzuki 3 figure 1c was a monumental event that was applauded by chemists worldwide.
The steric and electronic properties of the phosphorus ligands significantly impact the reactivity and outcome of palladiumcatalyzed cross coupling reactions. Pdcatalyzed suzuki coupling reaction of chloroalkylidene. The suzuki reaction is the coupling of an aryl or vinyl boronic acid with an aryl or. Toward green, cheap and environmentally friendly catalysis chun ho lam 2nd november, 2011 1. Q phos are highly successful for both electronpoor and electronrich aryl bromides and chlorides table 3. Prior to the event, wherever and whenever chemists met, these names, of course among select others, were frequently overheard as potential candidates since their discoveries laid the foundations of the field of palladiumcatalyzed cross coupling. Review on green chemistry suzuki cross coupling in aqueous. This reaction is used to create carboncarbon bonds to produce. Suzuki cross coupling reaction is one of the most famous reaction in the field of chemistry. Apr 29, 20 the suzuki coupling reaction is one of the most practiced classes of catalytic cc bond formation.
A highly enantioselective palladiumwjphoscatalyzed suzukimiyaura coupling reaction for efficient construction of axially chiral biaryl monophosphine oxides was developed. The suzuki reaction is the coupling of an aryl or vinyl boronic acid with an aryl or vinyl halide or triflate using a palladium catalyst. Fast suzuki miyaura cross coupling reaction with hexacationic triarylphosphine bndendriphos as ligand. Catalyzed suzuki coupling reaction of chloroalkylidenelactones with lb. In evaluating the hydrophobic phosphines utilized in the suzuki coupling, the neopentyl derivatives of ttbp tritertbutylphosphine were investigated. A highly efficient precatalytic system xphospdg2 for. Design and synthesis of phosphine ligands for pallaiumcatalyzed coupling reactions by william scott brown a dissertation submitted in partial fulfillment of the requirements for the doctor of philosophy in the department of chemistry in the graduate school of the university of alabama tuscaloosa, alabama 2009. Hindered biaryls and substrates containing a variety of functional groups can be prepared. Among many synthetic applications of suzuki coupling reaction for conjugated alkadienes, the total synthesis of palytoxin figure 2, a complex and toxic natural product is an epochmaking contribution kishi.
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