Synthesis of Donor-Acceptor Substituted Molecular Caltrops: Strategic Use of an AB₃ Synthon Based on a Tetraphenylmethane Core

Abstract

Using a tetraphenylmethane based AB₃ tecton, a facile synthetic route to donor-acceptor substituted unsymmetrical mole­cular caltrops is described. The former compound was readily prepared in two steps from the cheap commercial dye New Fuchsin.

Key words

molecular caltrops - dyad - tetraphenylmethane - Sonogashira coupling - Heck reaction

References

• 1a Turro NJ. Modern Molecular Photochemistry   Benjamin-Cumming; Menlo Park CA: 1978. 
• 1b Fox MA. Chanon M. Photoinduced Electron Transfer   Elsevier; Amsterdam: 1988. 
• 1c Gust D. Moore TA. Adv. Photochem.  1991,  16:  1 
• 1d Kavarnos GJ. Fundamentals of Photoinduced Electron Transfer   VCH; Weinheim: 1993. 
• 1e Gust D. Moore TA. Moore AL. Acc. Chem. Res.  1993,  26:  198 
• 1f Häder D.-P. Photosynthese   Thieme; Stuttgart: 1999. 
• 2a Guldi DM. Maggini M. Scorrano G. Prato M. J. Am. Chem. Soc.  1997,  119:  974 
• 2b Jolliffe KA. Langford SJ. Ranasinghe MG. Shephard M. Padden-Row MN. J. Org. Chem.  1999,  64:  1238 
• 2c Imahori H. Tamaki K. Guldi DM. Luo C. Fujitsuka M. Ito O. Sakata Y. Fukuzumi S. J. Am. Chem. Soc.  2001,  123:  2607 
• 2d Sakomura M. Lin S. Moore TA. Moore AL. Gust D. Fujihira M. J. Phys. Chem. A  2002,  106:  2218 ; and references cited therein
• 3a Vögtle F. Plevoets M. Nieger M. Azzellini GC. Credi A. De Cola L. De Marchis V. Venturi M. Balzani V. J. Am. Chem. Soc.  1999,  121:  6290 
• 3b Ceroni P. Vicinelli V. Maestri M. Balzani V. Müller WM. Müller U. Hahn U. Osswald F. Vögtle F. New J. Chem.  2001,  25:  989 
• 4a Reichert VR. Mathias LJ. Macromolecules  1994,  27:  7030 
• 4b Möngin O. Goassauer A. Tetrahedron  1997,  53:  6835 
• 4c Constable EC. Eich O. Housecroft CE. Johnstone LA. Chem. Commun.  1998,  2661 
• 4d Oldham WJ. Lahicotte RJ. Bazan GC. J. Am. Chem. Soc.  1998,  120:  2987 
• 4e Wang S. Oldham WJ. Hudack RA. Bazan GC. J. Am. Chem. Soc.  2000,  122:  5695 
• 4f Robinson MR. Wang S. Bazan GC. Cao Y. Adv. Mater.  2000,  12:  1701 
• 4g Constable EC. Eich O. Housecroft CE. Rees DC. Inorg. Chim. Acta  2000,  300-302:  158 
• 4h Zimmerman TJ. Freundel O. Gompper R. Müller TJJ. Eur. J. Org. Chem.  2000,  3305 
• 4i Aujard I. Baltaze J.-P. Baudin J.-B. Cogné E. Ferrage F. Jullien L. Perez E. Prévost V. Qian LH. Ruel O. J. Am. Chem. Soc.  2001,  123:  8177 
• 4j Lambert C. Gaschler W. Noll G. Weber M. Schmalzlin E. Brauchle C. Meerholz K. J. Chem. Soc., Perkin Trans. 2  2001,  964 
• 4k Yeh H.-C. Lee R.-H. Chan L.-H. Lin T.-YJ. Chen C.-T. Balasubramaniam E. Tao Y.-T. Chem. Mater.  2001,  13:  2788 
• 4l Maus M. De R. Lor M. Weil T. Mitra S. Wiesler UM. Herrman A. Hofkens J. Vosch T. Müllen K. De Schryver FC. J. Am. Chem. Soc.  2001,  123:  7668 
• 4m Weil T. Wiesler UM. Herrman A. Bauer R. Hofkens J. De Schryver FC. Müllen K. J. Am. Chem. Soc.  2001,  123:  8101 
• 4n Zimmerman TJ. Müller TJJ. Synthesis  2002,  1157 
• 4o Zimmerman TJ. Müller TJJ. Eur. J. Org. Chem.  2002,  2269 
• 4p Summers MA. Robinson MR. Bazan GC. Buratto SK. Chem. Phys. Lett.  2002,  364:  542 
• 4q Li Q. Rukavishnikov AV. Petukhov PA. Zaikova TO. Keana JFW. Org. Lett.  2002,  4:  3631 
• 4r Grimsdale AC. Bauer R. Weil T. Tchebotareva N. Wu J. Watson M. Müllen K. Synthesis  2002,  1229 
• 4s Sengupta S. Purkayastha P. Org. Biomol. Chem.  2003,  1:  436 ; and references cited therein
• For less common centrally tetrahedral scaffolds viz. 9,9′-spirobifluorene and tetraphenylsilane, see:
• 5a Tour JM. Chem. Rev.  1996,  96:  537 
• 5b Salbeck J. Yu N. Bauer J. Weissortel F. Bestgen H. Synth. Met.  1997,  91:  209 
• 5c Baurele P. Mitschke U. Mena-Osteritz E. Sokolowski M. Muller D. Grop M. Meerholz K. Proc. SPIE-Int. Soc. Opt. Engl.  1998,  3476:  32 
• 5d Pei J. Ni J. Zhou X.-H. Cao X.-Y. Lai Y.-H. J. Org. Chem.  2002,  67:  4924 
• 5e Chan L.-H. Lee R.-H. Hsieh C.-F. Yeh H.-C. Chen C.-T. J. Am. Chem. Soc.  2002,  124:  6469 
• 5f

  Also see ref. [4e]

• 6a Yao Y. Tour JM. J. Org. Chem.  1999,  68:  1968 
• 6b Hirayama D. Takiyama K. Aso Y. Otsubo T. Hasobe T. Yamada H. Imahori H. Fukuzumi S. Sakata Y. J. Am. Chem. Soc.  2002,  124:  532 
• 6c Galoppini E. Guo W. Zhang W. Hoertz PG. Qu P. Meyer GJ. J. Am. Chem. Soc.  2002,  124:  7801 
• 6d Piotrowiak P. Galoppini E. Wei Q. Meyer GJ. Weiwiór P. J. Am. Chem. Soc.  2003,  125:  5278 
• 6e Li Q. Rukavishnikov AV. Petukhov PA. Zaikova TO. Jin C. Keana JFW. J. Org. Chem.  2003,  68:  4862 
• 6f Jian H. Tour JM. J. Org. Chem.  2003,  68:  5091 
• 7a Sengupta S. Sadhukhan SK. Tetrahedron Lett.  1998,  39:  1237 
• 7b Sengupta S. Sadhukhan SK. Tetrahedron Lett.  1999,  40:  9157 
• 7c Sengupta S. Sadhukhan SK. Organometallics  2001,  20:  1889 
• 7d Sengupta S. Sadhukhan SK. Muhuri S. Tetrahedron Lett.  2002,  43:  3521 
• 7e Sengupta S. Sadhukhan SK. Singh RS. Indian J. Chem., Sect. B  2002,  41:  642 
• 7f Sengupta S. Sadhukhan SK. Indian J. Chem., Sect. B  2003,  42:  858 
• 8a Sengupta S. Sadhukhan SK. J. Mater. Chem.  2000,  1997 
• 8b Sengupta S. Sadhukhan SK. J. Chem. Soc., Perkin Trans. 1  2000,  4332 
• 10a Sonogashira K. In Comprehensive Organic Synthesis   Vol. 3:  Trost BM. Fleming I. Pergamon Press; Oxford: 1991.  p.551 
• 10b Sonogashira K. In Metal-catalyzed Cross-coupling Reactions   Diederich F. Stang P. Wiley-VCH; Weinheim: 1998.  p.203 
• 13a Jeffery T. Tetrahedron  1996,  52:  10113 
• 13b de Meijere A. Bräse S. In Metal-catalyzed Cross-coupling Reactions   Diederich F. Stang P. Wiley-VCH; Weinheim: 1998.  p.99 
• 13c Beletskaya IP. Cheprakov AV. Chem. Rev.  2000,  100:  3009 
• 15 Meier H. Angew. Chem., Int. Ed. Engl.  1992,  31:  1399 

9

Compound 5: mp 206-207 °C (MeOH). IR (KBr): 3400, 1605, 1500, 1460, 1370 cm^-1. ¹H NMR (300 MHz, CDCl₃/TMS): δ = 2.33 (s, 9 H), 6.65 (dd, J = 8.4, 2.1 Hz, 3 H), 6.70 (d, J = 6.6 Hz, 2 H), 6.99 (d, J = 6.6 Hz, 2 H), 7.02 (d, J = 2.1 Hz, 3 H), 7.65 (d, J = 8.4 Hz, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 28.2, 63.3, 98.7, 114.5, 130.1, 131.9, 138.0, 140.5, 146.5, 153.6.

11

Representative Procedure for Three-fold Sonogashira Couplings on 5: PdCl₂(PPh₃)₂ (5 mg) was added to a degassed solution of 5 (0.10 g, 0.13 mmol), phenyl acetylene (0.08 g, 0.8 mmol) and CuI (4 mg) in a mixture of DMF (3 mL) and Et₃N (2 mL). The reaction mixture was stirred at r.t. for 16 h. It was then concentratedd under reduced pressure, diluted with water and extracted with CH₂Cl₂. The organic layer was dried and the solvent removed under reduced pressure. The residue was purified by silica gel chromatography (10% EtOAc in light petroleum) to give 6 (0.057 g, 66%) as a white solid; mp 126-127 °C (CHCl₃-MeOH). IR (KBr): 3410, 1600, 1520, 1465, 1360 cm^-1. ¹H NMR (300 MHz, CDCl₃/TMS): δ = 2.43 (s, 9 H), 6.73 (d, J = 8.6 Hz, 2 H), 6.90-7.16 (m, 8 H), 7.29-7.48 (m, 12 H), 7.49-7.62 (m, 6 H). ¹³C NMR (75 MHz, CDCl₃): δ = 21.0, 64.5, 88.5, 93.8, 114.5, 121.2, 123.9, 125.6, 128.3, 128.7, 128.9, 130.1, 131.9, 132.2, 138.0, 139.5, 147.0, 156.5. 8: mp 105-106 °C (MeOH). IR (KBr): 3290, 3000, 2910, 2090, 1595, 1480 cm^-1. ¹H NMR (300 MHz, CDCl₃/TMS): δ = 2.35 (s, 9 H), 3.26 (s, 3 H), 6.71 (d, J = 8.7 Hz, 2 H), 6.93 (d, J = 8 Hz, 3 H), 7.00 (d, J = 8.7 Hz, 2 H), 7.01 (s, 3 H), 7.33 (d, J = 8 Hz, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 20.9, 64.0, 80.9, 82.3, 114.5, 119.6, 128.3, 131.7, 132.1, 138.0, 139.9, 147.0, 153.7.

12

Compound 9: mp 130-132 °C (MeOH). IR (KBr): 2916, 1596, 1521, 1500, 1442, 1344 cm^-1. ¹H NMR (300 MHz, CDCl₃/TMS): δ = 2.36 (s, 9 H), 5.08 (s, 2 H), 6.78 (d, J = 9 Hz, 2 H), 6.92 (dd, J = 8.1, 2 Hz, 3 H), 7.01 (d, J = 2 Hz, 3 H), 7.06 (d, J = 9 Hz, 2 H), 7.25-7.33 (m, 11 H), 7.42-7.46 (m, 6 H), 7.54 (d, J = 8.1 Hz, 3 H), 8.18 (d, J = 9 Hz, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 21.4, 64.5, 69.1, 88.5, 93.8, 114.2, 121.2, 123.9, 124.2, 128.0, 128.5, 128.7, 128.9, 131.3, 131.4, 131.9, 132.2, 132.6, 139.5, 139.8, 144.8, 147.0, 156.7.
Compound 10: mp 132-135 °C (MeOH). IR (KBr): 2900, 2100, 1590, 1518, 1487, 1350 cm^-1. ¹H NMR (300 MHz, CDCl₃/TMS): δ = 2.36 (s, 9 H), 3.24 (s, 3 H), 5.09 (s, 2 H), 6.73 (d, J = 9 Hz, 2 H), 6.91 (dd, J = 8, 1.8 Hz, 3 H), 7.00 (d, J = 1.8 Hz, 3 H), 7.06 (d, J = 9 Hz, 2 H), 7.30-7.36 (m, 5 H), 8.08 (d, J = 8.7 Hz, 2 H). Compound 13: mp 203-205 °C. IR (KBr): 2902, 1604, 1521, 1508, 1456, 1344, 1242 cm^-1. ¹H NMR (300 MHz, CDCl₃/TMS): δ = 1.33 (s, 27 H), 2.36 (s, 9 H), 5.16 (s, 2 H), 6.87 (d, J = 9 Hz, 2 H), 7.00 (d, J = 16.2 Hz, 3 H), 7.05-7.12 (m, 6 H), 7.24 (d, J = 9 Hz, 2 H), 7.28 (d, J = 16.2 Hz, 3 H), 7.35-7.53 (m, 14 H), 7.62 (d, J = 9 Hz, 3 H), 8.25 (d, J = 9 Hz, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 20.7, 31.7, 35.0, 64.1, 69.0, 114.0, 124.2, 124.4, 124.8, 125.8, 126.0, 126.6, 128.0, 129.5, 129.9, 130.3, 132.6, 133.1, 134.4, 135.1, 135.4, 140.5, 145.0, 146.4, 156.5.

14

Compound 11: mp 201-202 °C. IR (KBr): 3290, 1595, 1500, 1445, 1260 cm^-1. ¹H NMR (300 MHz, CDCl₃/TMS): δ = 2.35 (s, 9 H), 6.73 (d, J = 8.7 Hz, 2 H), 7.00 (d, J = 16.2 Hz, 3 H), 7.05-7.11 (m, 6 H), 7.14 (d, J = 8.7 Hz, 2 H), 7.20-7.31 (m, 6 H), 7.34 (d, J = 5.4 Hz, 3 H), 7.35 (d, J = 16.2 Hz, 3 H), 7.45-7.54 (m, 9 H). ¹³C NMR (75 MHz, CDCl₃): δ = 20.2, 63.7, 114.3, 124.4, 126.1, 126.5, 127.4, 128.6, 129.1, 129.7, 132.2, 132.7, 133.7, 134.7, 137.8, 139.2, 146.3, 153.4. Compound 12: mp 220-224 °C (CHCl₃-MeOH). IR (KBr): 3300, 1600, 1510, 1440, 1280 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 1.33 (s, 27 H), 2.34 (s, 9 H), 4.67 (br s, 1 H), 6.72 (d, J = 8.5 Hz, 2 H), 6.98 (d, J = 16 Hz, 3 H), 7.04-7.11 (m, 6 H), 7.14 (d, J = 8.3 Hz, 2 H), 7.26 (d, J = 16 Hz, 3 H), 7.37 (d, J = 8.2 Hz, 6 H), 7.45 (d, J = 8.8 Hz, 6 H), 7.48 (d, J = 9.2 Hz, 3 H).