Article
  • Synthesis of Frechet-type Dendrimers with Tripodal Core via Staudinger/Aza-Wittig Reactions
  • Han SC, Lee JW, Jin SH
  • Staudinger/Aza-Wittig 반응에 의한 삼발이 핵을 갖는 Frechet-type 덴드리머의 합성
  • 한승철, 이재욱, 진성호
Abstract
Efficient stitching methods for the synthesis of tripodal Frechet-type dendrimers containing secondary amine as a connector were elaborated. The synthetic strategy involved Staudinger/aza-Wittig reactions (new click reaction) between tripodal tris(azides) and aldehyde-dendrons in toluene in the presence of triphenylphosphine and followed by the reduction of imine intermediates. The tripodal core (1,3,5-tris-(3-azido-propoxy)-benzene) was chosen to serve as the azide functionalities for dendrimer growth. 1,3,5-Tris-(3-azido-propoxy)-benzene was stitched with the aldehyde-functionalized Frechet-type dendrons via Staudinger/aza-Wittig reactions leading to the formation of the corresponding Frechet-type dendrimers in high yields.

덴드리머의 중심에 삼발이 핵을 갖는 덴드리머의 합성을 위한 효율적인 연결 방법이 개발되었다. 합성전략은 알데히드 덴드론과 아자이드기를 갖는 삼발이 핵 사이의 반응을 톨루엔 용매와 triphenylphosphine 존재하에서 진행하는 새로운 클릭화학(Staudinger/aza-Wittig 반응)을 이용하였다. 덴드리머의 삼발이 핵으로 작용할 수 있는 단위체인 1,3,5-tris-(3-azido-propoxy)-benzene을 합성하였고, 이 화합물의 아자이드기는 덴드리머의 형성에 이용되었다. 1,3,5-Tris-(3-azido-propoxy)-benzene을 이용하여 알데히드 덴드론과 Staudinger/aza-Wittig 반응을 통해 덴드리머를 합성하 였으며, 모든 덴드리머는 높은 수득률로 얻어졌다.

Keywords: Staudinger/aza-Wittig reaction; aldehyde; azide; dendrimer; tripodal.

References
  • 1. Grimsdale AC, Mullen K, Angew. Chem. Int. Ed., 44, 5592 (2005)
  •  
  • 2. Tomalia DA, Prog. Polym. Sci., 30, 294 (2005)
  •  
  • 3. Grayson SM, Frechet JMJ, Chem. Rev., 101, 3919 (2001)
  •  
  • 4. Newkome GR, Moorefield CN, Vogtle F, Dendrimers and Dendrons: Concepts, Synthesis, Applications, Wiley-VCH, Weinheim (2001)
  •  
  • 5. Choi JS, Choi YH, Park JS, Bull. Korean Chem. Soc., 25, 1025 (2004)
  •  
  • 6. Kim TI, Jang HS, Joo DK, Choi JS, Park JS, Bull. Korean Chem. Soc., 24, 123 (2003)
  •  
  • 7. Palacios F, Alonso C, Aparicio D, Rubiales G, de los Santos JM, Tetrahedron, 63, 523 (2007)
  •  
  • 8. van Kalkeren HA, Grotenhuis C, Haasjes FS, Hommersom CA, Rutjes FPJT, van Delft FL, Eur. J. Org. Chem., 31, 7059 (2013)
  •  
  • 9. Menand M, Blais JM, Xie J, J. Org. Chem., 71, 3295 (2006)
  •  
  • 10. Miyake J, Chujo Y, Macromolecules, 41(24), 9677 (2008)
  •  
  • 11. Brase S, Gil C, Knepper K, Zimmermann V, Angew. Chem. Int. Ed., 44, 5188 (2005)
  •  
  • 12. Scriven EFV, Turnbull K, Chem. Rev., 88, 351 (1988)
  •  
  • 13. Lee JW, Kim BK, Bull. Korean Chem. Soc., 26, 658 (2005)
  •  
  • 14. Lee JW, Kim BK, Jin SH, Bull. Korean Chem. Soc., 26, 833 (2005)
  •  
  • 15. Lee JW, Kim JH, Kim BK, Shin WS, Jin SH, Tetrahedron, 62, 894 (2006)
  •  
  • 16. Lee JW, Lee UY, Han SC, Kim JH, Bull. Korean Chem. Soc., 30, 1001 (2009)
  •  
  • 17. Han SC, Jin SH, Lee JW, Bull. Korean Chem. Soc., 32, 3624 (2011)
  •  
  • 18. Han SC, Lee JW, Jin SH, Macromol. Res., 20(10), 1083 (2012)
  •  
  • 19. Grayson SM, Frechet JMJ, Chem. Rev., 101, 3919 (2001)
  •  
  • 20. Tozawa T, Chem. Commun., 1904 (2004)
  •  
  • 21. Liao LX, Stellacci F, McGrath DV, J. Am. Chem. Soc., 126(7), 2181 (2004)
  •  
  • 22. Hara M, Samori S, Cai XC, Tojo S, Arai T, Momotake A, Hayakawa J, Uda M, Kawai K, Endo M, Fujitsuka M, Majima T, J. Am. Chem. Soc., 126(43), 14217 (2004)
  •  
  • 23. Diez-Barra E, Gonzalez R, Sanchez-Verdu P, Tolosa J, Tetrahedron, 60, 1563 (2004)
  •  
  • 24. Momotake A, Arai T, Tetrahedron Lett., 45, 4131 (2004)
  •  
  • 25. Balzani V, Ceroni P, Giansante C, Vicinelli V, Klarner FG, Verhaelen C, Vogtle F, Hahn U, Angew. Chem. Int. Ed., 44, 4574 (2005)
  •  
  • 26. Li WS, Jiang DL, Suna Y, Aida T, J. Am. Chem. Soc., 127(21), 7700 (2005)
  •  
  • 27. Shanahan CS, McGrath DV, J. Org. Chem., 70, 1054 (2005)
  •  
  • 28. Lee JW, Kim BK, Jin SH, Bull. Korean Chem. Soc., 26, 715 (2005)
  •  
  • 29. Fresneda PM, Molina P, Synlett., 2004, 1 (2004)
  •  
  • 30. Eguchi S, Arkivoc, 2005, 98 (2005)
  •  
  • 31. Bellur E, Langer P, Tetrahedron Lett., 47, 2151 (2006)
  •  
  • 32. Menand M, Blais JC, Valery JM, Xie J, J. Org. Chem., 71, 3295 (2006)
  •  
  • 33. Mong TKK, Niu A, Chow HF, Wu C, Li L, Chen R, Chem. Eur. J., 7, 686 (2001)
  •  
  • 34. Sun H, Kaifer AE, Org. Lett., 7, 3845 (2005)
  •  
  • 35. Wong CH, Chow HF, Hui SK, Sze KH, Org. Lett., 8, 1811 (2006)
  •  
  • Polymer(Korea) 폴리머
  • Frequency : Bimonthly(odd)
    ISSN 0379-153X(Print)
    ISSN 2234-8077(Online)
    Abbr. Polym. Korea
  • 2023 Impact Factor : 0.4
  • Indexed in SCIE

This Article

  • 2014; 38(3): 386-390

    Published online May 25, 2014

  • Received on Jan 11, 2014
  • Accepted on Feb 9, 2014