Highly Regioselective Syntheses of Substituted Triphenylenes from 1,2,4-Trisubstituted Arenes via a Co-Catalyzed Intermolecular Alkyne Cyclotrimerization

Xu, Letian; Yu, Ruocheng; Wang, Yuefan; Chen, Jiahua; Yang, Zhen

doi:10.1021/jo400570b

Cited by 36 publications

(16 citation statements)

References 42 publications

(26 reference statements)

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“…261,262 Also, investigations for the synthesis of extended polycyclic materials, 263 such as 138, star-like polyarenes, 264 or chiral helicenes, 265,266 were reported. Intermolecular cyclotrimerisations of terminal alkynes to trisubstituted arenes (139) [267][268][269] as well as cyclotrimerisations of internal alkynes 270 were investigated to control the regiochemistry of the products, such as 140, formed. A cy-clotrimerisation reaction of an internal alkyne and a tetrayne starting material was investigated to generate a potentially axially chiral tetracyclic product 141.…”

Section: Syn Thesis 63 [2+2+2] Cycloadditionmentioning

confidence: 99%

Cobalt-Catalysed Bond Formation Reactions; Part 2

Röse

Hilt

2015

Synthesis

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This review summarises the cobalt-catalysed reactions of the years 2008 through 2014. Covered are addition reactions, such as the hydrogenation of double bonds, the addition of C-H bonds to double and triple bonds, C-H activation reactions, cobalt-catalysed cross-coupling reactions and selected additions of H-B and H-Si bonds to unsaturated starting materials. The cobalt-catalysed cycloadditions range from cyclopropanations, [2+2], Pauson-Khand reactions, [2+2+2], [4+2], [6+2] cycloadditions as well as benzannulations. Also covered are Nicholas reactions, cobalt-catalysed Jacobsen's kinetic resolution of epoxides as well as selected miscellaneous cobalt-catalysed processes mainly for carbon-carbon bond formations. 1 Introduction 2 Addition Reactions 3 Homo-and Cross-Coupling Reactions 4 Jacobsen Kinetic Resolution of Epoxides 5 Nicholas Reactions 6 Cycloaddition Reactions 7 Miscellaneous 8 Conclusion

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Section: Syn Thesis 63 [2+2+2] Cycloadditionmentioning

confidence: 99%

Cobalt-Catalysed Bond Formation Reactions; Part 2

Röse

Hilt

2015

Synthesis

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“…The spectroscopic data of 4h,i are consistent with those in previous literature. 25a 1,2,4-Tris(p-trifluoromethylphenyl)benzene (5f): 31 7, 125.2, 125.3, 125.4, 125.9, 127.1, 127.4, 12.9, 130.0, 130.1, 131.0, 131.4, 139.0, 139.9, 143.5, 144.0, 144.3; 19 F NMR (470.6 MHz, CDCl 3 ) δ −62.47, −62.48.…”

Section: ■ Conclusionmentioning

confidence: 99%

Syntheses of Arylphosphonium Salts from Cyclotrimerization of Terminal Aryl Alknyes by a Ruthenium Pentadienyl Complex and Revisiting the Catalytic Dimerization

Chen

Lin

2014

Organometallics

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The synthesis of polyaryl phosphonium salts by cyclotrimerization of aryl alkynes is induced by a stoichiometric amount of the ruthenium η 5 -pentadienyl complex (η 5 -C 5 H 7 )(PPh 3 ) 2 RuCl (1). With only 1 mol % quantity, complex 1 efficiently catalyzed the dimerization of aryl alkynes at room temperature to afford the corresponding (Z)-1,4-diarylbut-1-en-3-yne derivatives as the major products. ■ INTRODUCTIONResearch over several decades on transition-metal pentadienyl compounds has revealed significant differences in the steric and electronic properties between the η 5 -pentadienyl (C 5 H 7 ) and η 5 -cyclopentadienyl (C 5 H 5 or Cp) ligands in transition-metal compounds. 1 The two ligands are isoelectronic; however, the C 5 H 7 ligand (cone angle 180°), 2 which is both a better δ backbonding acceptor and a better σ donor than the Cp ligand, 1 is also sterically more demanding than the Cp ligand (cone angle 145°). 3 Calculations predict that η 5 to η 3 conversions in the C 5 H 7 ligand should be easier than that in a C 5 H 5 ligand. 1 These differences among C 5 H 7 , Cp, and indenyl (C 9 H 7 ) ligands are expected to influence various properties of their compounds. The potential ring slippage from η 5 to η 3 in the C 5 H 7 ligand that may possibly create novel catalytic reactivity in ruthenium metal complexes has been investigated. 4 Dimerization of a terminal aryl alkyne catalyzed by [Ru]-Cl (1, [Ru] = (η 5 -C 5 H 7 )(PPh 3 ) 2 Ru) concomitantly giving an unidentified brown powder was disclosed in 2007. 5 Aiming at understanding the chemistry of ruthenium pentadienyl species derived from alkyne, we explore the reactions of arylacetylene with 1. In this paper, we report a practical and switchable reaction system using either a stoichiometric or a catalytic quantity of 1, leading either to the synthesis of polyaryl phosphonium salts via cyclotrimerization or to dimerization of aryl alkynes under mild condition, respectively. ■ RESULTS AND DISCUSSIONTrimerization. Treatment of phenylacetylene (2a) with a stoichiometric quantity of 1 affords no ruthenium acetylide or vinylidene complexes which are generally formed from the reaction of the corresponding (η 5 -C 5 H 5 )(PPh 3 ) 2 RuCl complex. Instead, the reaction of 2a with 1 and KPF 6 , both in stoichiometric quantities, gives a brown powder as the major product. The previously reported catalytic dimerization of 2a by 1 without any additive 5 revealed a similar brown powder which displayed a singlet resonance at δ 25.5 in the 31 P NMR spectrum in low yield and was not fully characterized. Our product formed in the presence of KPF 6 shows a slightly different resonance at δ 23.0 and displays a set of peaks at δ −150 attributed to PF 6 − . The previously reported complex is believed to have a chloride counterion, instead of PF 6 − , thus showing slightly different 31 P NMR data. 5 The structure of our brown powder has been fully characterized by a single-crystal X-ray diffraction analysis as the polyaryl phosphonium salt 6a, resulting from addition of PPh 3 to...

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“…Cyclotrimerization of alkynes is a useful tool for synthesizing substituted benzene rings, especially those which are not easily assembled via conventional aromatic substitution reactions. Several catalysts containing Ti, Co, Ni, Ru and Rh have been reported to initialize cyclotrimerization reactions . Among these, Ni catalysts have advantages of being cheaper and having readily available reagents for complexation with a wide range of ligands.…”

Section: Introductionmentioning

confidence: 99%

Pd and Ni complexes of a novel vinylidene β‐diketimine ligand: Their application as catalysts in Heck coupling and alkyne trimerization

Raghavendra

Nareddula

2017

Applied Organom Chemis

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A β-diketimine ligand with vinylidene substitution at γ-carbon, CH 2 C(CH 3 CNAr) 2 (Ar = 2,6-diisopropylphenyl) (L 2 ), was synthesized by treating β-diketimine H 2 C(CH 3 CNAr) 2 with n-BuLi followed by paraformaldehyde. L 2 formed the homobimetallic ether-bridged β-diketiminate complex [O{(CH 2 -β-diketiminate) Pd(OAc)} 2 ] (1) with (PdOAc) 2 . It also gave complexes [L 2 PdCl 2 ] (2) and [L 2 NiBr 2 ] (3) when treated with PdCl 2 (CH 3 CN) 2 and NiBr 2 (dimethoxyethane), respectively. All the compounds were characterized using 1 H/ 13 C NMR spectroscopy and single-crystal X-ray diffraction studies. The catalytic activity of Pd and Ni complexes 1, 2 and 3 was explored in Heck coupling and alkyne trimerization reactions and it was found that they are very good catalysts. The results are reported in detail.

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Highly Regioselective Syntheses of Substituted Triphenylenes from 1,2,4-Trisubstituted Arenes via a Co-Catalyzed Intermolecular Alkyne Cyclotrimerization

Cited by 36 publications

References 42 publications

Cobalt-Catalysed Bond Formation Reactions; Part 2

Cobalt-Catalysed Bond Formation Reactions; Part 2

Syntheses of Arylphosphonium Salts from Cyclotrimerization of Terminal Aryl Alknyes by a Ruthenium Pentadienyl Complex and Revisiting the Catalytic Dimerization

Pd and Ni complexes of a novel vinylidene β‐diketimine ligand: Their application as catalysts in Heck coupling and alkyne trimerization

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