Alkyne complexes origins

Products 7a and 7c, with the substituent R a to the carbonyl group, are by far predominantly formed. This regioselectivity is a result of the preferential approach of the alkene 2 to the dicobalthexacarbonyl-alkyne complex 5 from the side opposite to the substituent R of the original alkyne. The actual incorporation of the alkene however is less selective with respect to the orientation of the olefinic substituent R, thus leading to a mixture of isomers 7a and 7c. 

Recently, Ohe and IJemura reported a novel approach to the catalytic cyclopropanation of alkenes via 2-furyl178 179 or 2-pyrrolyl carbenoids180 that originate from the intramolecular nucleophilic attack of a carbonyl oxygen or an imine nitrogen (ene-yne-ketone and ene-yne-imine precursor, respectively) on a 7t-alkyne complex or a cationic cr-vinyl complex. Initially, the group 6 complexes like Cr(CO)s were used. Soon it was found that a series of late transition... 

The isomerization, itself, originates from the a complex (B in Figure 3). However the total activation energy depends critically on the relative energy of A and B (Figure 3). An alkyne C=C triple bond binds more efficiently to a transition metal complex than a o C-H bond since the % C-C orbital is a better electron-donor and the 71 C-C orbital a better electron acceptor than the a and a C-H orbitals, respectively. However, the difference in energy between the two isomers is relatively low for a d6 metal center because four-electron repulsion between an occupied metal d orbital and the other n C-C orbital destabilizes the alkyne complex. This contributes to facilitate the transformation for the Ru11 system studied by Wakatsuki et al. 

In contrast to intramolecular cyclizations, the intermolecular addition of O-centered radicals to ti systems as initiating step in complex radical cyclization cascades has only recently attracted considerable attention. The reason for the low number of papers published on O radical addition to alkenes and alkynes could originate from the perception that O-centered radicals, such as alkoxyl radicals, RO, or acyloxyl radicals, RC(0)0", may not react with 7t systems through addition at rates that are competitive to other pathways, for example, allylic hydrogen abstraction and p-fragmentation in the case of RO" or decarboxylation in the case of RC(0)0" (Scheme 2.9). 

A reaction mechanism involving a transition metal was studied by Decker and Klobukowski218 who investigated the role of the acetylene ligand from a density functional perspective in M(CO)4(C2H2) (M = Fe, Ru or Os). Recent kinetics experiments have shown that the rate of CO substitution in complexes of the type M(CO)4(C2R2) is accelerated by factors of 102-1013 over their respective pentacarbonyl complexes. These substitution reactions have been shown to be dissociative in nature and show a marked metal dependence on the rate. The origin of the increased reactivity of these alkyne complexes was... 

The reaction between [Et20H][BF4] and the aminocaibynes trans-[M(CNMe)(sCNHMe)(dppe)2] BF4] (M = Mo, W) affords the alkyne complex r ww-[MF( n2-MeHNCsCNHMe)(dppe)2j[BF4], a compound originally formulated as a his-carbyne complex/29... 

The original Sonogashira reaction uses copper(l) iodide as a co-catalyst, which converts the alkyne in situ into a copper acetylide. In a subsequent transmeta-lation reaction, the copper is replaced by the palladium complex. The reaction mechanism, with respect to the catalytic cycle, largely corresponds to the Heck reaction.Besides the usual aryl and vinyl halides, i.e. bromides and iodides, trifluoromethanesulfonates (triflates) may be employed. The Sonogashira reaction is well-suited for the synthesis of unsymmetrical bis-2xy ethynes, e.g. 23, which can be prepared as outlined in the following scheme, in a one-pot reaction by applying the so-called sila-Sonogashira reaction ... 

The benzannulation reaction with small alkynes such as 1-pentyne may generate a two-alkyne annulation product. In this case the original [3+2+l]-benz-annulation is changed to a [2+2+1+1]-benzannulation. After CO dissociation and insertion of the first alkyne, the coordinated a,/J-unsaturated moiety in the vinylcarbene complex is supposed to be replaced by the second alkyne. The subsequent reaction steps give the phenol 112 (Scheme 50). 

What determines the propensity of cyclization of the different diethynylated complexes Looking carefully at the monomers, there are three variables which could influence the formation of cycles as opposed to linear polymers. One is the angle a between the two alkyne arms. The second is the parameter /, which indicates how far the two alkyne groups are apart at their origin, while the third is the parameter the bulk of the monomer. 

The carbene complexes generated by desulfurization of thioacetals with the titanoce-ne(II) species react with internal alkynes to produce the conjugated dienes 79 with high stereoselectivity (Scheme 14.34) [77]. The process appears to involve syn-elimination of P-hydride from the alkyl substituent that originates from the carbene complex after the formation of titanacyclobutene 80. 

The Dotz reaction mechanism has received further support from kinetic and theoretical studies. An early kinetic investigation [37] and the observation that the reaction of the metal carbene with the alkyne is supressed in the presence of external carbon monoxide [38] indicated that the rate-determining step is a reversible decarbonylation of the original carbene complex. Additional evidence for the Dotz mechanistic hyphotesis has been provided by extended Hiickel molecular orbital [23, 24] and quantum chemical calculations [25],... 

In spite of its simplicity and conceptual clearances, the original protocol has suffered from many intrinsic problems in a practical sense. For example, the reaction with the alkyne-cobalt complexes provided low chemical yields and required harsh reaction conditions. In addition, it was also difficult to extract the obtained product from the sticky metallic residue. Those problems can be accounted for based on the widely accepted mechanism given in Scheme 1, which, as proposed by Magnus," is supported by many theoretical studies. ... 

Alternatively, if, as was originally envisaged [157] the alkyne is adsorbed as a di-a-bonded complex (structure J), hydrogenation will lead to the direct formation of olefin in the gas phase. 

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