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Concise synthesis of α-substituted 2-benzofuranmethamines and other 2-subsituted benzofurans via α-substituted 2-benzofuranmethyl carbocation intermediates

Journal Article


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Abstract


  • Propargyl amines 4, where R3 is aryl, undergo 5-exo-dig cyclization reactions under relatively mild conditions (AgNO3, DMF, 60 °C, 1 h) to give 3-amino-2,3-dihydro-2-arylmethylidenebenzofurans 5 (R3 = aryl). In contrast, substrates where R3 is alkyl undergo competing 6-endo-dig and 5-exo-dig cyclization processes. The hydroxymethyl substrate 4 (R3 = CH2OH), however, was smoothly converted to its corresponding 5-exo-dig cyclization product 5, likely due to the assistance of the primary hydroxyl group in the 5-exo-dig cyclization process by silver cation coordination. Under more enforcing conditions (AgNO3, DMF, 100 °C, 18 h), the initially formed products 5 undergo a 1,3-allylic rearrangement to their corresponding 2-substituted benzofuran derivatives 6. This rearrangement can also be effected by treating 5 with AgNO3 in DMF at 100 °C for 18 h or BF3·Et2O at rt. 2-(3-Butenyl)benzofurans 7 (Nu = allyl) can be prepared by treatment of 5 with BF3·Et2O and allyltributylstannane. Furan and MeOH could also be employed as external nucleophiles in these BF3·Et2O-promoted reactions.

UOW Authors


  •   Wongsa, Nikhom (external author)
  •   Sommart, Ubonta (external author)
  •   Ritthiwigrom, Thunwadee (external author)
  •   Yazici, Arife (external author)
  •   Kanokmedhakul, Somdej (external author)
  •   Kanokmedhakul, Kwanjai (external author)
  •   Willis, Anthony C. (external author)
  •   Pyne, Stephen

Publication Date


  • 2013

Citation


  • Wongsa, N., Sommart, U., Ritthiwigrom, T., Yazici, A., Kanokmedhakul, S., Kanokmedhakul, K., Willis, A. C. & Pyne, S. G. (2013). Concise synthesis of α-substituted 2-benzofuranmethamines and other 2-subsituted benzofurans via α-substituted 2-benzofuranmethyl carbocation intermediates. Journal of Organic Chemistry, 78 (3), 1138-1148.

Scopus Eid


  • 2-s2.0-84873325933

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=1141&context=smhpapers

Ro Metadata Url


  • http://ro.uow.edu.au/smhpapers/142

Has Global Citation Frequency


Number Of Pages


  • 10

Start Page


  • 1138

End Page


  • 1148

Volume


  • 78

Issue


  • 3

Place Of Publication


  • United States

Abstract


  • Propargyl amines 4, where R3 is aryl, undergo 5-exo-dig cyclization reactions under relatively mild conditions (AgNO3, DMF, 60 °C, 1 h) to give 3-amino-2,3-dihydro-2-arylmethylidenebenzofurans 5 (R3 = aryl). In contrast, substrates where R3 is alkyl undergo competing 6-endo-dig and 5-exo-dig cyclization processes. The hydroxymethyl substrate 4 (R3 = CH2OH), however, was smoothly converted to its corresponding 5-exo-dig cyclization product 5, likely due to the assistance of the primary hydroxyl group in the 5-exo-dig cyclization process by silver cation coordination. Under more enforcing conditions (AgNO3, DMF, 100 °C, 18 h), the initially formed products 5 undergo a 1,3-allylic rearrangement to their corresponding 2-substituted benzofuran derivatives 6. This rearrangement can also be effected by treating 5 with AgNO3 in DMF at 100 °C for 18 h or BF3·Et2O at rt. 2-(3-Butenyl)benzofurans 7 (Nu = allyl) can be prepared by treatment of 5 with BF3·Et2O and allyltributylstannane. Furan and MeOH could also be employed as external nucleophiles in these BF3·Et2O-promoted reactions.

UOW Authors


  •   Wongsa, Nikhom (external author)
  •   Sommart, Ubonta (external author)
  •   Ritthiwigrom, Thunwadee (external author)
  •   Yazici, Arife (external author)
  •   Kanokmedhakul, Somdej (external author)
  •   Kanokmedhakul, Kwanjai (external author)
  •   Willis, Anthony C. (external author)
  •   Pyne, Stephen

Publication Date


  • 2013

Citation


  • Wongsa, N., Sommart, U., Ritthiwigrom, T., Yazici, A., Kanokmedhakul, S., Kanokmedhakul, K., Willis, A. C. & Pyne, S. G. (2013). Concise synthesis of α-substituted 2-benzofuranmethamines and other 2-subsituted benzofurans via α-substituted 2-benzofuranmethyl carbocation intermediates. Journal of Organic Chemistry, 78 (3), 1138-1148.

Scopus Eid


  • 2-s2.0-84873325933

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=1141&context=smhpapers

Ro Metadata Url


  • http://ro.uow.edu.au/smhpapers/142

Has Global Citation Frequency


Number Of Pages


  • 10

Start Page


  • 1138

End Page


  • 1148

Volume


  • 78

Issue


  • 3

Place Of Publication


  • United States