Palladium/copper-catalyzed cross-coupling

Tributylstannyl)-3-cyclobutene-1,2-diones and 4-methyl-3-(tributylstan-nyl)-3-cyclobutene-l,2-dione 2-ethylene acetals undergo the palladium/copper-catalyzed cross coupling with acyl halides, and palladium-catalyzed carbon-ylative cross coupling with aryl/heteroaryl iodides [45]. The coupling reaction of alkenyl (phenyl )iodonium triflates is also performed by a palladium/copper catalyst [46],... 

Waterlot, C., D. Couturier, and B. Rigo. 2000. Montmorillonite-palladium-copper catalyzed cross-coupling of methyl acrylate with aryl amines. Tetrahedron Lett. 41 317-319. 

The palladium-copper-catalyzed cross-coupling of acetylenic systems with aryl halide has been used successfully to homopolymerize p-bromoethynylbenzene (eq 4) [8]. The poly-p-ethynylbenzene was isolated as a white pol3nmer of relatively low molecular weight. The coupling of acetylenic reagents with aryl halides has been noted to lead to explosions and therefore due care should be exercised. 

In recent years, cross-coupling methodology has emerged as a viable tool for enamide synthesis, and, indeed, there are a number of published protocols which employ palladium- or copper-catalyzed stereospecific amidations of vinyl halides [17]. For example, Buchwald and coworkers had recently shown that a copper-catalyzed cross-coupling of vinyl bromides or iodides proceeded with retention of stereochemistry (Scheme 9.16), though the only example using a tetrasubstituted vinyl halide, 23, lacked the need for any stereochemical control in the halide portion [18]. Based on this it seemed feasible that the desired enamide 22 could potentially be assembled via a comparable coupling between amide 24 and a stere-odefined vinyl halide such as 25. 

Introduction of the silylmethyl group into organic halides, tosylates, and epoxides is achieved by nickel, palladium-, or copper-catalyzed cross-coupling reactions. 

Although palladium " and copper-catalyzed cross-coupling of amides and vinyl halides are possible, copper catalysis appears to be the most spread. On the basis of the precedents reported by Ogawa [150], Porco developed an efficient approach for the assembly of enamides using Liebeskind catalyst, copper(I) thiophene car-boxylate ([CuTC]), CS2CO3 and disubtituted ( )-vinyl iodides in NMP or DMSO. Using this protocol, a series of ( )-enamides could be prepared in moderate yields under mild conditions (Scheme 4.29) [144, 145]. Under these conditions, the coupling of 2-pyrrolidine and ( )-l-iodohept-l-ene takes place in 99 % yield. 

Abstract During the last decades a powerful set of protocols featuring C(sp )-N bond formation have emerged as convenient alternatives for the assembly of enamine and enamides. Those methods consist of mostly palladium-catalyzed oxidative amidations of alkenes and both palladium- and copper-catalyzed cross-couplings between generally vinyl halides or pseudohalides and amines or amides. In this review recent advances in both types of processes will be disclosed. Additionally, the synthetic value of the title processes will be illustrated by describing relevant total syntheses of natural products involving vinylation process as the key step. 

Pd/Cu-catalyzed cross-coupling of organohalides with terminal alkynes. Cf. Cadiot-Chodkiewicz coupling and Castro-Stephens reaction. The Castro-Stephens coupling uses stoichiometric copper, whereas the Sonogashira variant uses catalytic palladium and copper. 

Although there have been few new developments in the period since 1993, halogenopyrazines 42 have been convenient precursors for a variety of pyrazine derivatives. For example, the halogenopyrazines 42 are cyanated by palladium-catalyzed cross-coupling with alkali cyanide or by treatment with copper cyanide in refluxing picoline, to yield cyanopyrazines 48. Alkoxypyrazines 49 are produced by treatment with alkoxide-alcohol, and aminopyrazines 50 are prepared by amination with ammonia or appropriate amines. The nucleophilic substitution of chloropyrazine with sodium alkoxide, phenoxide, alkyl- or arylthiolate is efficiently effected under focused microwave irradiation <2002T887>. 

The synthesis of phosphino sulfoximine 97 relied significantly on the successful development of methods pursued in parallel in our group. Whereas palladium-catalyzed cross-couplings between 53 and 98 proceeded in low yield, the copper catalysis with a combination of copper(l) iodide and cesium acetate worked well, affording 99 in up to 83% yield [78]. The resulting phosphine oxides 99 were then reduced to the corresponding phosphines 97 using a mixture of trichlorosilane and triethylamine (Scheme 2.1.1.33). 

The mechanism of the Sonogashira reaction has not yet been established clearly. This statement, made in a 2004 publication by Amatore, Jutand and co-workers, certainly holds much truth [10], Nonetheless, the general outline of the mechanism is known, and involves a sequence of oxidative addition, transmetalation, and reductive elimination, which are common to palladium-catalyzed cross-coupling reactions [6b]. In-depth knowledge of the mechanism, however, is not yet available and, in particular, the precise role of the copper co-catalyst and the structure of the catalytically active species remain uncertain [11, 12], The mechanism displayed in Scheme 2 includes the catalytic cycle itself, the preactivation step and the copper mediated transfer of acetylide to the Pd complex and is based on proposals already made in the early publications of Sonogashira [6b]. 

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