Bonding alkynes

Many examples of insertions of internal alkynes are known. Internal alkynes react with aryl halides in the presence of formate to afford the trisubstituted alkenes[271,272]. In the reaction of the terminal alkyne 388 with two molecules of iodobenzene. the first step is the formation of the phenylacetylene 389. Then the internal alkyne bond, thus produced, inserts into the phenyl-Pd bond to give 390. Finally, hydrogenolysis with formic acid yields the trisubstituted alkene 391(273,274], This sequence of reactions is a good preparative method for trisubstituted alkenes from terminal alkynes. 

ADDITION OF ALCOHOLS, PHENOLS, AND THIOLS TO ALKENE AND ALKYNE BONDS... 

Addition reactions at the alkyne bonds are dealt with in the section on alkenylstannanes that are produced. The alkynyl-tin bond is more readily cleaved by both electrophiles and nucleophiles than is the alkenyl- or alkyl-tin bond. Strong electrophiles such as halogens or halogen acids attack at the z/Mzi-position of the triple bond to give a /3-stannyl cation that is stabilized by C-Sn hyperconjugation, but this is followed by cleavage of the C-Sn bond (Equation (83)). 

However, a crucial difference was seen in analogous reactions with the (tert-butyl)alkynylcarbene complex 184.a, carried out under a pressure of carbon monoxide. A [4 + 2] cycloaddition takes place, but in this case the ene fragment is not the alkyne functionality, but the carbene-alkyne bond. The mechanism presented by Park implies that this is due to the preliminary... 

Radical intermediates are also trapped by intramolecular reaction with an alkene or alkyne bond. At a mercury cathode this process competes with formation of the dialkylmercury [51], At a reticulated vitreous carbon cathode, this intramolecular cyclization of radicals generated by reduction of iodo compounds is an important process. Reduction of l-iododec-5-yne 5 at vitreous carbon gives the cyclopentane... 

The alkynes are bonded in essentially the same way as, but less firmly than, the olefins (see Section III,R). In the hex-3-yne series, substitution of an a-hydrogen atom by a methyl group reduces the argentation constant (a measure of the silver-alkyne bond strength) by a factor of roughly 1 /3 this influence of methyl substitution on complex formation is opposite to that observed in the platinum(II) complexes (see Section IV,J). 

For a full discussion of alkyne bond distances, see Simonetta Gavezzotti, Ref. 7. 

There seems to be consensus that a copper-alkyne bond is homolytically broken by oxygen (often just air) and the radicals thus formed, couple ... 

The effects of hydrogen on the infrared spectra of adsorbed acetylene together with evidence from mechanistic studies of alkyne hydrogenation has led to the general conclusion that the acetylenic species active in hydrogenation is associatively bonded to the surface. However, as with monoolefins, there is still doubt as to the precise formulation of the surface—alkyne bonding. In the early work [156], it was assumed that the associatively adsorbed complex was adequately represented as a di-a-bonded olefin, which adopted a cis-configuration. 

Alkyne complexes of Os(II) are observed to undergo addition of water and methanol across the alkyne bond, resulting in stable vinyl alcohol and vinyl ether complexes, respectively (168). When an aqueous solution of [Os(NH3)5(CH3C=CCH3)]2+ is allowed to stand, the initial product observed is the cis-2-hydroxy-2-butene complex. Over a period of several days, this species equilibrates with its trans stereoisomer, the latter being slightly favored in aqueous solution (Keq = 1.5). 

A theoretical approach addresses the question of alkynes bonded to PtL2 fragments in both parallel and perpendicular geometries. With each mode of alkyne coordination there is required a different coordination geometry at platinum. The authors use the isolobal analogy to calculate the electronic structures of complexes, and propose several unknown complexes to be stable.842... 

The term oxidative cyclization is based on the fact that two-electron oxidation of the central metal occurs by the cyclization. The same reaction is sometimes called reductive cyclization . This term is based on alkene or alkyne bonds, because the alkene double bond in 13 is reduced to the alkane bond 14, and the alkyne 15 bond is reduced to the alkene bond 16 by the cyclization. Cyclizations of alkynes and alkenes catalyzed by transition metal complexes proceed by oxidative cyclization. In particular, low-valent complexes of early transition metals have a high tendency to obtain the highest possible oxidation state, and hence they react with alkynes and alkenes forming rather stable metallacycles by oxidative addition or oxidative cyclization. 

The reaction of Co2(CO)8 with alkynes in an organic solvent affords stable complexes 201. Two 7i-bonds of the alkyne bond coordinate to two Co atoms, respectively and its structure is shown by 203. However, in this section the simplified form 204 is used for simplicity. When complex 201 is heated with alkene, the... 

As regards the protecting effect, the complex is stable to Lewis acids. Also, no addition of BH3 occurs. As Co2(CO)6 can not coordinate to alkene bonds, selective protection of the triple bond in enyne 137 is possible, and hydroboration or diimide reduction of the double bond can be carried out without attacking the protected alkyne bond to give 138 and 139 [32], Although diphenylacetylene cannot be subjected to smooth Friedcl Crafts reaction on benzene rings, facile /7-acylation of the protected diphenylacetylene 140 can be carried out to give 141 [33], The deprotection can be effected easily by oxidation of coordinated low-valent Co to Co(III), which has no ability to coordinate to alkynes, with CAN, Fe(III) salts, amine /V-oxidc or iodine. 

In this publication the author describes the phenomenon that most times the thermodynamically less stable product (see 29) of the two possible rings (e.g. 5-exo and 6-endo) is formed. Today looking at the 5-exo cyclization it is known that, although the generated primary radical is less stable than a secondary one, stereoelectronic effects favor reaction to the kinetically controlled product. According to MO-calculations, for a successful cyclization, an angle of 70° of the incoming radical to the plane of the alkene-/alkyne-bond is necessary.11... 

Apart from the construction of phenanthrenes, carbene complexes have also been used for the synthesis of more extended polycyclic arenes. An unusual dimerization of chromium coordinated ortbo-ethynyl aryl carbenes results in the formation of chrysenes (Scheme 37) [81]. This unusual reaction course is presumably due to the rigid C2 bridge that links the carbene and alkyne moieties, and thus prevents a subsequent intramolecular alkyne insertion into the metal-carbene bond. Instead, a double intermolecular alkyne insertion favored by the weak chromium-alkyne bond is believed to occur forming a central ten-membered ring that may then rearrange to the fused arene system. For example, under typical benzannulation conditions, carbene complex 97 affords an equimolar mixture of chrysene 98a and its monochromium complex 98b. The peri-interactions between the former alkyne substituent (in the 5- and 11-positions) and the aryl hydrogen induce helicity in the chrysene skeleton. 

The catalyst [RuC12(CO)3]2 also promotes the electrophilic activation of the C=CH bond of co-arylalk-l-ynes. The intramolecular cycloisomerization takes place with nucleophilic addition of the aryl group to the activated /1-carbon of the alkyne bond, thus eliminating a vinylidene intermediate [68]. 

The metal-alkyne bonding parameters of molecules of the type CpML-(RC=CR)X are similar to those of other classes of four-electron donor alkynes in Table I. Both cationic and neutral derivatives with cyclopen-tadienyl (Cp = t75-C5H5) or indenyl (tj5-C9H7) illustrate the structural regularities of these molecules. The preponderance of molybdenum derivatives relative to tungsten reflects more extensive and diverse synthetic chemistry with molybdenum to date. 

---