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Volumn 14, Issue 22, 2008, Pages 6697-6703

Palladium-catalyzed formation of highly substituted naphthalenes from arene and alkyne hydrocarbons

Author keywords

Alkynes; C H activation; C P cleavage; Crystal engineering; Cyclization; Naphthalene; Palladium

Indexed keywords

ACETYLENE; HYDROCARBONS; NETWORK PROTOCOLS; ORGANIC COMPOUNDS; ORGANIC POLYMERS; ORGANOMETALLICS; PALLADIUM; SILVER;

EID: 53849118099     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200800538     Document Type: Article
Times cited : (98)

References (94)
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    • Although several synthetic routes to highly substituted naphthalenes have been reported, none of them involve direct aryl C-H bond activations. For reactions of alkynes with triphenylchromium through a benzochromacyclopentadiene intermediate, see: a G. M. Whitesides, W. J. Ehmann, J. Am. Chem. Soc. 1970, 92, 5625;
    • Although several synthetic routes to highly substituted naphthalenes have been reported, none of them involve direct aryl C-H bond activations. For reactions of alkynes with triphenylchromium through a benzochromacyclopentadiene intermediate, see: a) G. M. Whitesides, W. J. Ehmann, J. Am. Chem. Soc. 1970, 92, 5625;
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    • Acetoxystilbene and/or its hydrolysis product deoxybenzoin were obtained in some cases. The former compound should be formed from 1,2-diphenylethyne (2 a) by the hydroacetoxylalion. For examples of metal-catalyzed/mediated hydroacetoxylation of alkynes, see: a) N. Menashe, Y. Shvo, J. Org. Chem. 1993, 58, 7434;
    • Acetoxystilbene and/or its hydrolysis product deoxybenzoin were obtained in some cases. The former compound should be formed from 1,2-diphenylethyne (2 a) by the hydroacetoxylalion. For examples of metal-catalyzed/mediated hydroacetoxylation of alkynes, see: a) N. Menashe, Y. Shvo, J. Org. Chem. 1993, 58, 7434;
  • 43
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    • A monitored experiment indicated that naphthalene 3aa was not generated from 3 sa by Pd-catalyzed denomination.
    • A monitored experiment indicated that naphthalene 3aa was not generated from 3 sa by Pd-catalyzed denomination.
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    • See ref. [13h] and references therein. For a recent review, see: b R. A. Pascal. Jr., Chem. Rev. 2006, 106, 4809.
    • a) See ref. [13h] and references therein. For a recent review, see: b) R. A. Pascal. Jr., Chem. Rev. 2006, 106, 4809.
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    • The end-to-end twist of compound 3ea (23.9°) is very close to that of perchloronaphthalene (24°), see: F. H. Herbslein, Acta Crystallogr. Sect. B 1979, 35, 1661.
    • The end-to-end twist of compound 3ea (23.9°) is very close to that of perchloronaphthalene (24°), see: F. H. Herbslein, Acta Crystallogr. Sect. B 1979, 35, 1661.
  • 46
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    • CCDC-668637 (3ea), 648605 (3ga), and 671871 (3ac) contain the supplementary crystallography data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
    • CCDC-668637 (3ea), 648605 (3ga), and 671871 (3ac) contain the supplementary crystallography data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
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    • p-1,1,3,3-tet-ramethylbutylcalix[4]-arene/toluene: b) G. D. Andreetti, A. Pochini and R. Ungaro, J. Chem. Soc. Perkin Trans. 2 1983, 1773. p-tert-batylcalix[6]arene/toluene:
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    • X-ray crystallography tends to underestimate the conformation of the methyl group. If the methyl C-H bond length and the bond angle CCH is assumed to be 1.07 Åand 109.5°. respectively, then the distance of methyl hydrogen atom to the tetraphenylbenzo plane is approximately between 2.52 and 2.97 Å.
    • X-ray crystallography tends to underestimate the conformation of the methyl group. If the methyl C-H bond length and the bond angle CCH is assumed to be 1.07 Åand 109.5°. respectively, then the distance of methyl hydrogen atom to the tetraphenylbenzo plane is approximately between 2.52 and 2.97 Å.
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    • 3-CH-fullerene interaction is 2.87 ± 0.13 Å, see:
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    • Several Pd catalysts have been found to produce hexasubstituted benzenes, such as 6, by the [2+2+2] cyclotrimerzation of internal alkynes 2, with a palladacyclopentadiene of type 5 as a key intermediate, see: a Y.-S. Fu, S. J. Yu, Angew. Chem. 2001, 113, 451;
    • Several Pd" catalysts have been found to produce hexasubstituted benzenes, such as 6, by the [2+2+2] cyclotrimerzation of internal alkynes 2, with a palladacyclopentadiene of type 5 as a key intermediate, see: a) Y.-S. Fu, S. J. Yu, Angew. Chem. 2001, 113, 451;
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    • 0, species is the reactive form for a [2+2+2] cycloaddilion, see: d) T. Yokota, Y. Sakurai, S. Sakaguchi, Y. Ishii, Tetrahedron Lett. 1997, 38, 3923.
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    • An organopalladium(IV) intermediate similar to complex 5 has been delected, see: a) R. van Belzen, H. Hoffmann, C. J. Elsevier, Angew. Chem. 1997, 109, 1833;
    • An organopalladium(IV) intermediate similar to complex 5 has been delected, see: a) R. van Belzen, H. Hoffmann, C. J. Elsevier, Angew. Chem. 1997, 109, 1833;
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    • p-Xylene (2 mL; 16.2 mmol) is used in large excess with respect to 2a (1.5 mmol) in these reactions.
    • p-Xylene (2 mL; 16.2 mmol) is used in large excess with respect to 2a (1.5 mmol) in these reactions.
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    • Compound 11 has been previously characterized as a twisted molecule, see: R. A. Pascal, Jr., D. van Engen, B. Kahr, W. D. McMillan, J. Org. Chem. 1988, 53, 1687.
    • Compound 11 has been previously characterized as a twisted molecule, see: R. A. Pascal, Jr., D. van Engen, B. Kahr, W. D. McMillan, J. Org. Chem. 1988, 53, 1687.
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    • Traces of hexamethyl benzenehexacarboxylate were also isolated (entry 28 in Table 2).
    • Traces of hexamethyl benzenehexacarboxylate were also isolated (entry 28 in Table 2).
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    • In the presence of Lewis acids, hexaarylbenzenes undergo oxidative intramolecular cyclodehydrogenation to form hexa-peri-hexabenzocoronenes. For reviews, see: a M. D. Watson, A. Fechtenkötter, K. Müllen, Chem. Rev. 2001, 101, 1267;
    • In the presence of Lewis acids, hexaarylbenzenes undergo oxidative intramolecular cyclodehydrogenation to form hexa-peri-hexabenzocoronenes. For reviews, see: a) M. D. Watson, A. Fechtenkötter, K. Müllen, Chem. Rev. 2001, 101, 1267;
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    • According to the Aldrich catalogue (USA, 2007-2008), triphenylphosphine (USD 35.1/mol) (USD = US dollars)is less expensive than iodobenzene (USD 49.8/mol) and o-diiodobenzene (USD 4719/ mol). The last two compounds have been used for the preparation of 3ba, see ref. [13].
    • According to the Aldrich catalogue (USA, 2007-2008), triphenylphosphine (USD 35.1/mol) (USD = US dollars)is less expensive than iodobenzene (USD 49.8/mol) and o-diiodobenzene (USD 4719/ mol). The last two compounds have been used for the preparation of 3ba, see ref. [13].
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    • For metal-mediated or -catalyzed C-P bond cleavage of organophosphorus species, see: a
    • For metal-mediated or -catalyzed C-P bond cleavage of organophosphorus species, see: a) V. V. Grushin, Organometallics 2000, 19, 1888;
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    • 0-catalyzed reactions of quaternary phosphonium halides with olefins, organoboranes, and alkynes, see: a L. K. Hwang, Y. Na, J. Lee, Y. Do, S. Chang, Angew. Chem. 2005, 117, 6322;
    • 0-catalyzed reactions of quaternary phosphonium halides with olefins, organoboranes, and alkynes, see: a) L. K. Hwang, Y. Na, J. Lee, Y. Do, S. Chang, Angew. Chem. 2005, 117, 6322;
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    • 0 species and triphenylphosphine oxide, see: C. Amatore, E. Carre, A. Jutand, M. A. M'Barki, Organometallics 1995, 14, 1818.
    • 0 species and triphenylphosphine oxide, see: C. Amatore, E. Carre, A. Jutand, M. A. M'Barki, Organometallics 1995, 14, 1818.
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    • Triphenylphosphine oxide cannot generate 3ba.
    • Triphenylphosphine oxide cannot generate 3ba.
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    • 53849142954 scopus 로고    scopus 로고
    • 3] within 10 min in > 90% yield.
    • 3] within 10 min in > 90% yield.
  • 92
    • 53849095199 scopus 로고    scopus 로고
    • Reaction of [Ag(PPh3)2]NO3 with alkyne 2a in our catalytic system Cu(OAc)2.H2O (2 equiv, Na 2[PdCl6].4H2O (8 mol , AgNO3 (1.2 equiv, and pyridine (2.4 equiv) in CH3CN at 110°C for 36 h gave 3ba in 48% yield (based on PPh3; 96% yield based on [Ag-(PPh3)2]NO3, In the absence of the additional AgNO3. 3ba 24, can also be isolated
    • 3. 3ba (24%) can also be isolated.
  • 93
    • 53849087902 scopus 로고    scopus 로고
    • A preliminary study indicated that naphthalene 3ia displays aggregation-induced emission (M. Y. Kuo, Y. T. Wu unpublished results).
    • A preliminary study indicated that naphthalene 3ia displays aggregation-induced emission (M. Y. Kuo, Y. T. Wu unpublished results).


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