Alkynes interconversions

Similarly to alkenes, alkynes react with various titanium-methylidene precursors, such as the Tebbe reagent [13,63], titanacydobutanes [9b, 64], and dimethyltitanocene [65] to form the titanium-containing unsaturated cyclic compounds, titanacydobutenes 67 (Scheme 14.29). Alternatively, 2,3-diphenyltitanacydobutene can be prepared by the reaction of the complex titanocene(II) bis(trimethylphosphine) with 1,2-diphenylcyclopropene [66]. Substituent effects in titanacydobutenes [67], the preparation of titanocene-vinylke-tene complexes by carbonylation of titanacydobutenes [68], and titanacyclobutene-vinylcar-bene complex interconversion [69] have been investigated. 

All metal vinylidenes described herein are derived from alkynes. While alkyne-to-vinylidene interconversion typically occurs via the 1,2-shift of a hydrogen atom, the corresponding migration of heavier main group heteroatoms is also possible. 

The ability to harness alkynes as effective precursors of reactive metal vinylidenes in catalysis depends on rapid alkyne-to-vinylidene interconversion [1]. This process has been studied experimentally and computationally for [MC1(PR3)2] (M = Rh, Ir, Scheme 9.1) [2]. Starting from the 7t-alkyne complex 1, oxidative addition is proposed to give a transient hydridoacetylide complex (3) vhich can undergo intramolecular 1,3-H-shift to provide a vinylidene complex (S). Main-group atoms presumably migrate via a similar mechanism. For iridium, intermediates of type 3 have been directly observed [3]. Section 9.3 describes the use of an alternate alkylative approach for the formation of rhodium vinylidene intermediates bearing two carbon-substituents (alkenylidenes). 

The Lee group originated rhodium alkenylidene-mediated catalysis by combining acetylide/alkenylidene interconversion with known metal vinylidene functionalization reactions [31], Thus, the first all-intramolecular three-component coupling between alkyl iodides, alkynes, and olefins was realized (Scheme 9.17). Prior to their work, such tandem reaction sequences required several distinct chemical operations. The optimized reaction conditions are identical to those of their original two-component cycloisomerization of enynes (see Section 9.2.2, Equation 9.1) except for the addition of an external base (Et3N). Various substituted [4.3.0]-bicyclononene derivatives were synthesized under mild conditions. Oxacycles and azacycles were also formed. The use of DMF as a solvent proved essential reactions in THF afforded only enyne cycloisomerization products, leaving the alkyl iodide moiety intact. 

The intermediacy of a platinum vinylidene in Yamamoto s reaction was supported by the results of isotopic labeling studies. D FT calculations were used to further probe the proposed reaction mechanism. In contrast to the prevailing model of alkyne/ vinylidene interconversion for Rh(I)-catalysts, direct Ca Cp 1,2-H-migration is implicated in the formation of vinylidene 130. Direct C—H insertion via a single... 

Cyclic alkynes (C9, Ci0, or Cn) also rearrange in the presence of bases to an equilibrium mixture containing cyclic allene [43]. The bases used were NaNH2-liq. NH3 at -33.4°C, KOH-C2H5OH at 131°-134°C (sealed tubes), KO-f-Bu-f-BuOH at 79.4°-l 20.0°C (sealed tubes) [44]. A solution of sodamide in liquid ammonia gave the most rapid ( to 3 hr) allene-acetylene interconversions of all systems examined. 

The process may be reversed by treating 2-alkynes with sodium to get 1-alkynes after acidification of the product. The presence of an alkyl substituent at C(3) of a 1-alkyne prevents its isomerization to the corresponding 2-alkyne. Instead, an allene is formed [Eq. (4.27)]. This observation led to the suggestion of the involvement of allene intermediates to interpret the shift of the triple bond in the interconversion of acetylenes [Eq. (4.28)] ... 

The mechanism Favorskii envisioned involved the initial attack of the ethoxy anion on the triple bond to form a vinyl ether. The now accepted carbanionic mechanism assumes the formation of resonance-stabilized anions, allowing the stepwise interconversion of 1- and 2-alkynes, and allenes143 147 (Scheme 4.9). 

Rapid development of this area followed the discovery of routes to these complexes, either by ready conversion of terminal alkynes to vinylidene complexes in reactions with manganese, rhenium, and the iron-group metal complexes (11-14) or by protonation or alkylation of some metal Recent work has demonstrated the importance of vinylidene complexes in the metabolism of some chlorinated hydrocarbons (DDT) using iron porphyrin-based enzymes (15). Interconversions of alkyne and vinylidene ligands occur readily on multimetal centers. Several reactions involving organometallic reagents may proceed via intermediate vinylidene complexes. 

Theoretical and experimental studies on the reaction of 3,4-bis(methoxycarbonyl)-1,2-dithiete with alkenes and alkynes yielding cycloadducts have been carried out. The activation energy of the interconversion of the 1,2-dithiete to 1,2-dithione was estimated by MO calculations. These calculations (MP2/6-31G(d)) show that the dithiete 19f is 5.8 kcal mol-1 more stable than the ethane-1,2-dithione cis-20f, and the tautomerization energy is 28.5 kcal mol-1 from the thiete 19f and this value of the activation energy supports the possibility of the tautomerization between the 1,2-dithiete 19f and ethane-1,2-dithione cis-20f, at least at high temperature <1996IJQ859>. 

Bisalkyne cyclopentadienyl derivatives of molybdenum and tungsten have been prominent in the development of Group VI alkyne chemistry in the 1980s. Unlike the dithiocarbamate systems where addition of a second alkyne produces a substitutionally inert bisalkyne derivative, interconversion of monoalkyne and bisalkyne cyclopentadienyl complexes is facile and synthetically useful. 

Rotational barriers have been probed for a number of bisalkyne complexes (Table VII). Cationic [CpM(RC=CR)2(CO)]+ complexes exhibit relatively high barriers (16-21 kcal/mol). Both standard variable-temperature NMR techniques (94) and two-dimensional methods (162) have been used to elucidate isomer interconversion schemes with two unsymmetrical alkynes in the coordination sphere. The plane of symmetry present when two symmetrical alkynes bind to a CpMX fragment is not retained in all isomers with RC=CH ligands. The availability of distal and proximal alkyne termini locations relative to the adjacent cis ligand leads to two cis isomers (R and R near one another) and one trans isomer (Fig. 25). Rotation of only one alkyne ligand converts cis to trans and vice versa, but direct cis to cis conversion is not possible unless both alkynes rotate simultaneously. 

They may be readily transformed to r] -aUcynyl and vinylidene complexes. The coupling of two ) -alkynyl ligands results in platinacyclopentadiene species." A platinum(II) disilyl( -alkyne) undergoes insertion (see Insertion) and reductive elimination (see Reductive Elimination) to disilacyclohexene (Scheme 31)." Metal-diaUcynyls can also play jr-donors to form the coordination complexes of various configurations, as shown in (10-13) and so on." Such a,tt-bridging modes may have interconversion. Multi- aUcynyl complexes can even constitute clusters or higher-order stractures. ... 

B. Functional Groups — Preparation, reactions, and interconversions of alkanes, alkenes, alkynes, dienes, alkyl halides, alcohols, ethers, epoxides, sulfides, thiols, aromatic compounds, aldehydes, ketones, carboxylic acids and their derivatives, amines... 

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