Linear trimerization of 1‐ethynylcyclohexan‐1‐ol catalysed by nickel(II) complexes

Carusi, Paola; Cerichelli, Giorgio; Furlani, A.; Russo, Maria Vittoria; Suber, Lorenza

doi:10.1002/aoc.590010610

Cited by 11 publications

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“…The stereochemistry of 7 should be determined by the cis -stereochemistry of the insertion steps. Although catalytic oligomerizations of alkynes such as linear oligomerization giving oligoenyne compounds and cyclic oligomerization of alkynes giving, for example, benzene and cyclooctatriene derivatives have many precedents, to our knowledge only two examples of linear trimerization appeared, as reported by Klein and Furlani …”

Section: Resultsmentioning

confidence: 88%

Synthesis and Characterization of Coordinatively Unsaturated Alkynyl- and Aryl-Cobalt Complexes with 15 Valence Electrons, Tpⁱ^Pr2Co−R, Bearing the Hydrotris(3,5-diisopropylpyrazolyl)borato Ligand (Tpⁱ^Pr2)

2002

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Coordinatively unsaturated 15e alkynyl- (Tp i Pr2Co−C⋮C−R) and aryl-cobalt complexes (Tp i Pr2Co-aryl) bearing the hydrotris(3,5-diisopropylpyrazolyl)borato ligand (Tp i Pr2) are prepared by dehydrative condensation of the hydroxo complex [Tp i Pr2Co(μ-OH)2]2 with 1-alkyne and arylation of the chloro complex Tp i Pr2Co−Cl with Grignard reagents, respectively. Spectroscopic and crystallographic analyses reveal the apparent C 3-symmetrical tetrahedral structures with high-spin electronic configuration (S = 3/2), which should result from the property of the Tp i Pr2 ligand as a tetrahedral enforcer. The Tp i Pr2Co and hydrocarbyl fragments are connected dominantly through σ-bonding interaction, and π-interaction including back-donation is not significant as revealed by EHMO calculations. The Co−C bonds are so polarized as to be readily protonated even by moisture to give the corresponding hydrocarbons, but the reactivity toward unsaturated hydrocarbons turns out to be sluggish. Tp i Pr2Co−C⋮C−COOMe is found to catalyze a rare example of specific linear trimerization of methyl propiolate to give (E,E)-MeOOC(H)CCH−CHC(COOMe)−C⋮C−COOMe.

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Section: Resultsmentioning

confidence: 88%

Synthesis and Characterization of Coordinatively Unsaturated Alkynyl- and Aryl-Cobalt Complexes with 15 Valence Electrons, Tpⁱ^Pr2Co−R, Bearing the Hydrotris(3,5-diisopropylpyrazolyl)borato Ligand (Tpⁱ^Pr2)

2002

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“…Usually alkynes (and propargyl alcohols) undergo cyclotrimerization on dicobalt complexes 23 forming 1,2,4-or 1,3,5-substituted benzenes. Linear oligomerization of three molecules of ECY in the presence of nickel has also been reported: 24 of these, two are bound tail-to-tail and the third one head-to-tail. Interestingly, no dehydration, neither loss of OH nor of "O", has been observed in this process.…”

Section: Reaction Pathwaysmentioning

confidence: 91%

Activation of alkynols on transition metal carbonyl clusters. Reactions of 1-ethynylcyclohexanol with Fe3(CO)12 and Co2(CO)8. Crystal structures of Co3(CO)9[μ3-CCH2(C6H10OH)], Fe3(CO)9(μ-CO)[μ3-η2-CC(C6H10)] and Co2Fe(CO)6(μ-CO)[μ3-η7-(C6H9)CC(H)C(H)C(H)(C6H10)]

Gatto

Gervasio

Marabello

et al. 2001

J. Chem. Soc., Dalton Trans.

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The reactions of Co 2 (CO) 8 with 1-ethynylcyclohexanol (HC᎐ ᎐ ᎐ CC 6 H 10 OH, ECY) in benzene led mainly to Co 2 (CO) 6 (ECY) 1 and to smaller amounts of the methylidyne complex Co 3 (CO) 9 [µ 3-CCH 2 (C 6 H 10 OH)] 2. The reactions of Fe 3 (CO) 12 with ECY in the same solvent led to binuclear metallacyclic derivatives Fe 2 (CO) 6 (ECY) 2 (isomers 3a, 3b) or Fe 2 (CO) 6 [(ECY) 2 Ϫ H 2 O] 3c as the main products; small yields of trinuclear complexes Fe 3 (CO) 9 (µ-CO)[µ 3-η 2-1,2-HC᎐ ᎐ ᎐ C(C 6 H 10 OH)] 4, Fe 3 (CO) 9 (µ-CO)[µ 3-η 2-1,2-C᎐ ᎐ C(C 6 H 10)] 5 and Fe 3 (CO) 7-[µ 3-η 7-(C 6 H 10 OH)CCHCHC(C 6 H 9)] 6 {containing respectively a parallel alkynol, an allenylidene and a dimeric metallacyclic ligand} were also obtained, together with 7, a thermal decomposition product of 6. Finally, when Co 2 (CO) 8 was treated with ECY in benzene, and Fe 3 (CO) 12 was added, the heterometallic complex Co 2 Fe(CO) 6-(µ-CO)[µ 3-η 7-(C 6 H 9)CC(H)C(H)C(H)(C 6 H 10)] 8 was obtained in low yields. The complexes have been characterized by means of IR and 1 H NMR spectroscopies and by mass spectrometry. The structures of 2, 5, 8 have been determined by X-ray diffraction. Complex 2 contains an "hydrogenated" ECY ligand, 5 an allenylidene ligand formed upon dehydration of ECY (loss of the OH and of the terminal hydrogen), whereas 8 contains a ligand formed by tail-to-tail coupling of two ECY molecules, with loss of water and oxygen and shift of hydrogen. The elemental analysis of complex 8 gave a Co : Fe ratio of 2 : 1; on the basis of this analysis, the refinement of the diffraction data allowed a hypothesis on the distribution of the metal atoms in the cluster. Reaction pathways for the formation of these clusters are proposed and dehydration mechanisms for the ligand discussed.

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Cotrimerizations of Acetylenic Compounds

et al. 2007

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The cyclotrimerization of acetylenic compounds is a useful method for the construction of three new bonds in a one‐step process. Although symmetry‐allowed, there is a paucity of examples of purely thermal [2+2+2] cycloadditions. The first example reported was in 1866, which was the cyclization of acetylene to benzene. High temperatures are required for this reaction and a mixture of products is formed. In 1948, Reppe discovered the first transition‐metal catalyzed version of this reaction in which nickel was used and substituted benzenes were formed. Since then catalysts based on transition metals, lanthanides, actinide, and aluminum have been developed for the cycloaddition of substituted alkynes to benzene derivatives. Many compounds can take part in the cyclization reactions to give four‐, five‐,six, or eight membered rings. Many of these reactions have found many applications in organic synthesis This chapter is devoted to early to late transition metal‐mediated cotrimerization of acetylenic compounds directed towards organic synthesis. It addresses the scope and generality of the reaction, as well as the current state of the art, with regard to region‐and stereoselectivities. In the context of selectivity, a mechanistic overview is provided. Inter‐and intramolecular versions of the cyclizations are presented with an emphasis on applications in synthesis. The literature up to mid‐2004 is covered.

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Linear trimerization of 1‐ethynylcyclohexan‐1‐ol catalysed by nickel(II) complexes

Abstract: The catalytic reaction of 1-ethynylcyclohexan-1-01 (EC) in the presence of bisphosphine nickel([[) complexes yields a linear trimer. The trimer could be isolated and characterized by means of MS, IR and NMR spectroscopies. The reaction mechanism is also discussed.

Cited by 11 publications

References 11 publications

Synthesis and Characterization of Coordinatively Unsaturated Alkynyl- and Aryl-Cobalt Complexes with 15 Valence Electrons, Tpⁱ^Pr2Co−R, Bearing the Hydrotris(3,5-diisopropylpyrazolyl)borato Ligand (Tpⁱ^Pr2)

Synthesis and Characterization of Coordinatively Unsaturated Alkynyl- and Aryl-Cobalt Complexes with 15 Valence Electrons, Tpⁱ^Pr2Co−R, Bearing the Hydrotris(3,5-diisopropylpyrazolyl)borato Ligand (Tpⁱ^Pr2)

Activation of alkynols on transition metal carbonyl clusters. Reactions of 1-ethynylcyclohexanol with Fe3(CO)12 and Co2(CO)8. Crystal structures of Co3(CO)9[μ3-CCH2(C6H10OH)], Fe3(CO)9(μ-CO)[μ3-η2-CC(C6H10)] and Co2Fe(CO)6(μ-CO)[μ3-η7-(C6H9)CC(H)C(H)C(H)(C6H10)]

Cotrimerizations of Acetylenic Compounds

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Linear trimerization of 1‐ethynylcyclohexan‐1‐ol catalysed by nickel(II) complexes

Abstract: The catalytic reaction of 1-ethynylcyclohexan-1-01 (EC) in the presence of bisphosphine nickel([[) complexes yields a linear trimer. The trimer could be isolated and characterized by means of MS, IR and NMR spectroscopies. The reaction mechanism is also discussed.

Cited by 11 publications

References 11 publications

Synthesis and Characterization of Coordinatively Unsaturated Alkynyl- and Aryl-Cobalt Complexes with 15 Valence Electrons, TpiPr2Co−R, Bearing the Hydrotris(3,5-diisopropylpyrazolyl)borato Ligand (TpiPr2)

Synthesis and Characterization of Coordinatively Unsaturated Alkynyl- and Aryl-Cobalt Complexes with 15 Valence Electrons, TpiPr2Co−R, Bearing the Hydrotris(3,5-diisopropylpyrazolyl)borato Ligand (TpiPr2)

Activation of alkynols on transition metal carbonyl clusters. Reactions of 1-ethynylcyclohexanol with Fe3(CO)12 and Co2(CO)8. Crystal structures of Co3(CO)9[μ3-CCH2(C6H10OH)], Fe3(CO)9(μ-CO)[μ3-η2-CC(C6H10)] and Co2Fe(CO)6(μ-CO)[μ3-η7-(C6H9)CC(H)C(H)C(H)(C6H10)]

Cotrimerizations of Acetylenic Compounds

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Synthesis and Characterization of Coordinatively Unsaturated Alkynyl- and Aryl-Cobalt Complexes with 15 Valence Electrons, Tpⁱ^Pr2Co−R, Bearing the Hydrotris(3,5-diisopropylpyrazolyl)borato Ligand (Tpⁱ^Pr2)

Synthesis and Characterization of Coordinatively Unsaturated Alkynyl- and Aryl-Cobalt Complexes with 15 Valence Electrons, Tpⁱ^Pr2Co−R, Bearing the Hydrotris(3,5-diisopropylpyrazolyl)borato Ligand (Tpⁱ^Pr2)