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Volumn 59, Issue 45, 2003, Pages 8859-8868

Pt(IV)-catalyzed cyclization of arene-alkyne substrates via C-H bond functionalization

Author keywords

Alkynes; Benzopyrans; C H activation; C H fuctionalization; Chromenes; Hydroarylation; Platinum(IV)

Indexed keywords

ALKENE DERIVATIVE; ALKYL GROUP; ALKYNE; AMINE; CARBON; COUMARIN DERIVATIVE; ESTER DERIVATIVE; ETHER DERIVATIVE; GALLIUM; HALIDE; HYDROGEN; HYDROXYL GROUP; METHYL GROUP; PALLADIUM; PLATINUM; POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVE; QUINOLINE DERIVATIVE;

EID: 0142248466     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tet.2003.05.003     Document Type: Article
Times cited : (160)

References (48)
  • 6
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    • Historically, the term 'C-H bond activation' carries considerable mechanistic claim while 'C-H bond functionalization' simply describes a formal process. Consequently, in the case of arenes, the term 'C-H activation' should be used thoughtfully since other mechanistic modes are readily available, for instance, electrophilic metallation (substitution)
    • Historically, the term 'C-H bond activation' carries considerable mechanistic claim while 'C-H bond functionalization' simply describes a formal process. Consequently, in the case of arenes, the term 'C-H activation' should be used thoughtfully since other mechanistic modes are readily available, for instance, electrophilic metallation (substitution).
  • 15
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    • (a) There is yet another mechanistic possibility involving hydrometallation of triple carbon-carbon bond, generating an alkenyl metal species, followed by intramolecular substitution of the arene ring. Hydropalladation has been proposed to be the first step in the intermolecular cyclization of alkynoate esters and phenols. (b) See also (a) There is yet another mechanistic possibility involving hydrometallation of triple carbon-carbon bond, generating an alkenyl metal species, followed by intramolecular substitution of the arene ring. Hydropalladation has been proposed to be the first step in the intermolecular cyclization of alkynoate esters and phenols Trost B.M., Toste F.D. J. Am. Chem. Soc. 118:1996;6305. (b) See also Larock R.C., Dotty M.J., Tian Q., Zenner J.M. J. Org. Chem. 62:1997;7536.
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    • (a) There is yet another mechanistic possibility involving hydrometallation of triple carbon-carbon bond, generating an alkenyl metal species, followed by intramolecular substitution of the arene ring. Hydropalladation has been proposed to be the first step in the intermolecular cyclization of alkynoate esters and phenols. (b) See also (a) There is yet another mechanistic possibility involving hydrometallation of triple carbon-carbon bond, generating an alkenyl metal species, followed by intramolecular substitution of the arene ring. Hydropalladation has been proposed to be the first step in the intermolecular cyclization of alkynoate esters and phenols Trost B.M., Toste F.D. J. Am. Chem. Soc. 118:1996;6305. (b) See also Larock R.C., Dotty M.J., Tian Q., Zenner J.M. J. Org. Chem. 62:1997;7536.
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    • (a) Ref. 10.
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    • (a) Ref. 9.
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    • 4, the former being more efficient in many cases. (a) Fürstner A., Stelzer F., Szillat H. J. Am. Chem. Soc. 123:2001;11863 (b) Méndez M., Paz Muñoz M., Nevado C., Cárdenas D.J., Echavarren A.M. J. Am. Chem. Soc. 123:2001;10511 (c) Blum, J.; Beer-Kraft, H.; Badrieh, Y. J. Org. Chem. 1995, 60, 5567. (d) Kobayashi S., Kakumoto K., Sugiura M. Org. Lett. 4:2002;1319.
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    • 4, the former being more efficient in many cases. (a) Fürstner A., Stelzer F., Szillat H. J. Am. Chem. Soc. 123:2001;11863 (b) Méndez M., Paz Muñoz M., Nevado C., Cárdenas D.J., Echavarren A.M. J. Am. Chem. Soc. 123:2001;10511 (c) Blum, J.; Beer-Kraft, H.; Badrieh, Y. J. Org. Chem. 1995, 60, 5567. (d) Kobayashi S., Kakumoto K., Sugiura M. Org. Lett. 4:2002;1319.
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    • 4, the former being more efficient in many cases. (a) Fürstner A., Stelzer F., Szillat H. J. Am. Chem. Soc. 123:2001;11863 (b) Méndez M., Paz Muñoz M., Nevado C., Cárdenas D.J., Echavarren A.M. J. Am. Chem. Soc. 123:2001;10511 (c) Blum, J.; Beer-Kraft, H.; Badrieh, Y. J. Org. Chem. 1995, 60, 5567. (d) Kobayashi S., Kakumoto K., Sugiura M. Org. Lett. 4:2002;1319.
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    • 4, the former being more efficient in many cases. (a) Fürstner A., Stelzer F., Szillat H. J. Am. Chem. Soc. 123:2001;11863 (b) Méndez M., Paz Muñoz M., Nevado C., Cárdenas D.J., Echavarren A.M. J. Am. Chem. Soc. 123:2001;10511 (c) Blum, J.; Beer-Kraft, H.; Badrieh, Y. J. Org. Chem. 1995, 60, 5567. (d) Kobayashi S., Kakumoto K., Sugiura M. Org. Lett. 4:2002;1319.
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    • For complete screening, see supporting information in Ref. 7
    • For complete screening, see supporting information in Ref. 7.
  • 33
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    • Direct cycloaddition of propargyl alcohols with phenols have been reported. However, these methods do not provide access to chiral chromenes with asymmetric control: (a). For other synthetic approaches to chromenes, see: (c). and references therein. For syntheses of fused polycyclic arenes via cyclization of 2-alkynylbiaryls: (d). and references therein Direct cycloaddition of propargyl alcohols with phenols have been reported. However, these methods do not provide access to chiral chromenes with asymmetric control: (a) Bigi F., Carloni S., Maggi R., Muchetti C., Sartori G. J. Org. Chem. 62:1997;7024 (b) Nishibayashi Y., Inada Y., Hidai M., Uemura S. J. Am. Chem. Soc. 124:2002;7900. For other synthetic approaches to chromenes, see: (c) Portscheller J.L., Malinakova H.C. Org. Lett. 4:2002;3679. and references therein. For syntheses of fused polycyclic arenes via cyclization of 2-alkynylbiaryls: (d) Goldfinger M.B., Crawford K.B., Swager T.M. J. Am. Chem. Soc. 119:1997;4578. and references therein.
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    • Bigi, F.1    Carloni, S.2    Maggi, R.3    Muchetti, C.4    Sartori, G.5
  • 34
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    • Direct cycloaddition of propargyl alcohols with phenols have been reported. However, these methods do not provide access to chiral chromenes with asymmetric control: (a). For other synthetic approaches to chromenes, see: (c). and references therein. For syntheses of fused polycyclic arenes via cyclization of 2-alkynylbiaryls: (d). and references therein Direct cycloaddition of propargyl alcohols with phenols have been reported. However, these methods do not provide access to chiral chromenes with asymmetric control: (a) Bigi F., Carloni S., Maggi R., Muchetti C., Sartori G. J. Org. Chem. 62:1997;7024 (b) Nishibayashi Y., Inada Y., Hidai M., Uemura S. J. Am. Chem. Soc. 124:2002;7900. For other synthetic approaches to chromenes, see: (c) Portscheller J.L., Malinakova H.C. Org. Lett. 4:2002;3679. and references therein. For syntheses of fused polycyclic arenes via cyclization of 2-alkynylbiaryls: (d) Goldfinger M.B., Crawford K.B., Swager T.M. J. Am. Chem. Soc. 119:1997;4578. and references therein.
    • (2002) J. Am. Chem. Soc. , vol.124 , pp. 7900
    • Nishibayashi, Y.1    Inada, Y.2    Hidai, M.3    Uemura, S.4
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    • 0011825560 scopus 로고    scopus 로고
    • Direct cycloaddition of propargyl alcohols with phenols have been reported. However, these methods do not provide access to chiral chromenes with asymmetric control: (a). For other synthetic approaches to chromenes, see: (c). and references therein. For syntheses of fused polycyclic arenes via cyclization of 2-alkynylbiaryls: (d). and references therein Direct cycloaddition of propargyl alcohols with phenols have been reported. However, these methods do not provide access to chiral chromenes with asymmetric control: (a) Bigi F., Carloni S., Maggi R., Muchetti C., Sartori G. J. Org. Chem. 62:1997;7024 (b) Nishibayashi Y., Inada Y., Hidai M., Uemura S. J. Am. Chem. Soc. 124:2002;7900. For other synthetic approaches to chromenes, see: (c) Portscheller J.L., Malinakova H.C. Org. Lett. 4:2002;3679. and references therein. For syntheses of fused polycyclic arenes via cyclization of 2-alkynylbiaryls: (d) Goldfinger M.B., Crawford K.B., Swager T.M. J. Am. Chem. Soc. 119:1997;4578. and references therein.
    • (2002) Org. Lett. , vol.4 , pp. 3679
    • Portscheller, J.L.1    Malinakova, H.C.2
  • 36
    • 0030962531 scopus 로고    scopus 로고
    • Direct cycloaddition of propargyl alcohols with phenols have been reported. However, these methods do not provide access to chiral chromenes with asymmetric control: (a). For other synthetic approaches to chromenes, see: (c). and references therein. For syntheses of fused polycyclic arenes via cyclization of 2-alkynylbiaryls: (d). and references therein Direct cycloaddition of propargyl alcohols with phenols have been reported. However, these methods do not provide access to chiral chromenes with asymmetric control: (a) Bigi F., Carloni S., Maggi R., Muchetti C., Sartori G. J. Org. Chem. 62:1997;7024 (b) Nishibayashi Y., Inada Y., Hidai M., Uemura S. J. Am. Chem. Soc. 124:2002;7900. For other synthetic approaches to chromenes, see: (c) Portscheller J.L., Malinakova H.C. Org. Lett. 4:2002;3679. and references therein. For syntheses of fused polycyclic arenes via cyclization of 2-alkynylbiaryls: (d) Goldfinger M.B., Crawford K.B., Swager T.M. J. Am. Chem. Soc. 119:1997;4578. and references therein.
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    • Goldfinger, M.B.1    Crawford, K.B.2    Swager, T.M.3
  • 37
    • 85030955655 scopus 로고    scopus 로고
    • 49 was subjected to these reaction conditions and no deuterium incorporation was observed
    • In a control experiment 49 was subjected to these reaction conditions and no deuterium incorporation was observed.
  • 38
    • 85030955373 scopus 로고    scopus 로고
    • To the best of our knowledge a 6-endo Heck cyclization of propargly-aryl ethers, or amines is unprecedented
    • To the best of our knowledge a 6-endo Heck cyclization of propargly-aryl ethers, or amines is unprecedented.
  • 40
    • 85030971338 scopus 로고    scopus 로고
    • 2, 9% of the 6-exo product was obtained along with 16% of compound 59
    • 2, 9% of the 6-exo product was obtained along with 16% of compound 59.


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