Metal insertion cyclotrimerization

Pd-cataly2ed reactions of butadiene are different from those catalyzed by other transition metal complexes. Unlike Ni(0) catalysts, neither the well known cyclodimerization nor cyclotrimerization to form COD or CDT[1,2] takes place with Pd(0) catalysts. Pd(0) complexes catalyze two important reactions of conjugated dienes[3,4]. The first type is linear dimerization. The most characteristic and useful reaction of butadiene catalyzed by Pd(0) is dimerization with incorporation of nucleophiles. The bis-rr-allylpalladium complex 3 is believed to be an intermediate of 1,3,7-octatriene (7j and telomers 5 and 6[5,6]. The complex 3 is the resonance form of 2,5-divinylpalladacyclopentane (1) and pallada-3,7-cyclononadiene (2) formed by the oxidative cyclization of butadiene. The second reaction characteristic of Pd is the co-cyclization of butadiene with C = 0 bonds of aldehydes[7-9] and CO jlO] and C = N bonds of Schiff bases[ll] and isocyanate[12] to form the six-membered heterocyclic compounds 9 with two vinyl groups. The cyclization is explained by the insertion of these unsaturated bonds into the complex 1 to generate 8 and its reductive elimination to give 9. 

A wide variety of homogeneous and heterogeneous catalysts are available for alkyne cyclotrimerization. As a result, numerous mechanistic pathways have been established for the different versions of this process, each characteristic of the metals involved in the system. The most common involves the intermediacy of metallacyclopentadienes, derived as already shown from any number of metal fragments and two alkynes. Upon opening a vacant coordination site, these systems may readily complex a third alkyne, which may insert to give a transient metallacycloheptatriene from which the benzene product is ultimately released via reductive elimination of the metal (Scheme 24). ... 

Finally, transition metal-catalyzed reactions of arynes have been explored as a useful method for the construction of a wide variety of carbo- and heteocycles. These reactions include cyclotrimerization of arynes, cocyclization of arynes with alkynes or alkenes, and carbopaUadation of arynes with Pd-complexes. Moreover, some insertion reactions of arynes into a-bonds are also catalyzed by metal complexes. 

Most transition-metal-mediated alkyne cyclotrimerizations proceed via the general mechanism, which is known as the common mechanism and involves the initial formation of a metallacyclopentadiene intermediate (A) by the oxidative cychzation of two alkyne molecules on a low-valent metal center (Scheme 3.19) [69], The metallacyclopentadiene intermediate then possibly reacts with a third alkyne molecule via insertion to produce metallacycloheptatriene B, which yields the final aromatic product by subsequent reductive elimination. Alternatively, metallacyclopentadiene A undergoes [4 + 2] cycloaddition with an alkyne to produce metallanorbornadiene C [70]. 

The cyclic process can be illustrated by acetylene cyclotrimerization to benzene by a transition metal in a low oxidation state. At the first stage, two acetylene molecules give the five-membered cycle involving the central M atom, and the insertion of the third acetylene molecule increases the number of atoms in the cycle to seven followed by the rearrangement to benzene... 

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