Direct Photoinduced Electron Transfer from Excited State of Rhodamine B for Carbon-Radical Generation

Abstract

The photoinduced electron transfer (PIET) from the excited singlet state (S ₁) of rhodamine B to i-C₃F₇I smoothly proceeded in the presence of water. This process was supported by the fluorescence quenching of rhodamine B with addition of i-C₃F₇I in ethanol. The present method was applied to the atom-transfer radical reaction involving the cyclization step.

Key words

radical reaction - cyclization - photochemistry - alkyl halides - fluorine

• References and Notes


For reviews, see:
• 1a Narayanam JM. R, Stephenson CR. J. Chem. Soc. Rev. 2011; 40: 102
• 1b Tucker JW, Stephenson CR. J. J. Org. Chem. 2012; 77: 1617
• 1c Ischay MA, Yoon TP. Eur. J. Org. Chem. 2012; 3359
• 1d Shi L, Xia W. Chem. Soc. Rev. 2012; 41: 7687
• 1e Hari DP, König B. Angew. Chem. Int. Ed. 2013; 52: 4734
• 1f Zou Y.-Q, Chen J.-R, Xiao W.-J. Angew. Chem. Int. Ed. 2013; 52: 11701
• 1g Ravelli D, Fagnoni M, Albini A. Chem. Soc. Rev. 2013; 42: 97
• 1h Yoon TP. ACS Catal. 2013; 3: 895
• 1i Nicewicz DA, Nguyen TM. ACS Catal. 2014; 4: 355
• 2 Turro NJ. Modern Molecular Photochemistry . University Science Books; Mill Valley: 1991
• 3 Klán P, Wirz J. Photochemistry of Organic Compounds: From Concept to Practice. Wiley; West Sussex: 2009

Acridinium salts could be classified into another type. See:
• 4a Grandjean J.-MM, Nicewicz DA. Angew. Chem. Int. Ed. 2013; 52: 3967
• 4b Hamilton DS, Nicewicz DA. J. Am. Chem. Soc. 2012; 134: 18577
• 5 Zhao J, Wu W, Sun J, Guo S. Chem. Soc. Rev. 2013; 42: 5323
• 6a Senaweera SM, Singh A, Weaver JD. J. Am. Chem. Soc. 2014; 136: 3002
• 6b Qvortrup K, Rankic DA, MacMillan DW. C. J. Am. Chem. Soc. 2014; 136: 626
• 6c Nakajima M, Lefebvre Q, Rueping M. Chem. Commun. 2014; 50: 3619
• 6d Jiang H, Cheng Y, Wang R, Zheng M, Zhang Y, Yu S. Angew. Chem. Int. Ed. 2013; 52: 13289
• 6e Zhu S, Das A, Bui L, Zhou H, Curran DP, Rueping M. J. Am. Chem. Soc. 2013; 135: 1823
• 6f Miyazawa K, Yasu Y, Koike T, Akita M. Chem. Commun. 2013; 49: 7249
• 6g Miyake Y, Nakajima K, Nishibayashi Y. J. Am. Chem. Soc. 2012; 134: 3338
• 6h Wallentin C.-J, Nguyen JD, Finkbeiner P, Stephenson CR. J. J. Am. Chem. Soc. 2012; 134: 8875
• 6i Nguyen JD, Tucker JW, Konieczynska MD, Stephenson CR. J. J. Am. Chem. Soc. 2011; 133: 4160
• 6j Nagib DA, Scott ME, MacMillan DW. C. J. Am. Chem. Soc. 2009; 131: 10875
• 7a Farney EP, Yoon TP. Angew. Chem. Int. Ed. 2014; 53: 793
• 7b Hari DP, Hering T, König B. Angew. Chem. Int. Ed. 2014; 53: 725
• 7c Huang H, Zhang G, Gong L, Zhang S, Chen Y. J. Am. Chem. Soc. 2014; 136: 2280
• 7d Maity S, Zheng N. Angew. Chem. Int. Ed. 2012; 51: 9562
• 7e Cai S, Zhao X, Wang X, Liu Q, Li Z, Wang DZ. Angew. Chem. Int. Ed. 2012; 51: 8050
• 7f DiRocco DA, Rovis T. J. Am. Chem. Soc. 2012; 134: 8094
• 7g Chen M, Huang Z.-T, Zheng Q.-Y. Chem. Commun. 2012; 48: 11686
• 7h Zhao G, Yang C, Guo L, Sun H, Chen C, Xia W. Chem. Commun. 2012; 48: 2337
• 7i Zou Y.-Q, Lu L.-Q, Fu L, Chang N.-J, Rong J, Chen J.-R, Xiao W.-J. Angew. Chem. Int. Ed. 2011; 50: 7171
• 7j Larraufie M.-H, Pellet R, Fensterbank L, Goddard J.-P, Lacôte E, Malacria M, Ollivier C. Angew. Chem. Int. Ed. 2011; 50: 4463
• 7k Kalyani D, McMurtrey KB, Neufeldt SR, Sanford MS. J. Am. Chem. Soc. 2011; 133: 18566
• 7l Ischay MA, Anzovino ME, Du J, Yoon TP. J. Am. Chem. Soc. 2008; 130: 12886
• 7m Narayanam JM. R, Tucker JW, Stephenson CR. J. J. Am. Chem. Soc. 2009; 131: 8756
• 7n Nicewicz DA, MacMillan DW. C. Science 2008; 322: 77
• 8a Meng Q.-Y, Zhong J.-J, Liu Q, Gao X.-W, Zhang H.-H, Lei T, Li Z.-J, Feng K, Chen B, Tung C.-H, Wu L.-Z. J. Am. Chem. Soc. 2013; 135: 19052
• 8b Zhang J, Wang L, Liu Q, Yang Z, Huang Y. Chem. Commun. 2013; 49: 11662
• 8c Majekz M, von Wangelin AJ. Chem. Commun. 2013; 49: 5507
• 8d Hari DP, Schroll P, König B. J. Am. Chem. Soc. 2012; 134: 2958
• 9a For tetrabutylammonium decatungstate, see: Ryu I, Tani A, Fukuyama T, Ravelli D, Fagnoni M, Albini A. Angew. Chem. Int. Ed. 2011; 50: 1869
• 9b For Rose Bengal, see: Kalaitzakis D, Montagnon T, Alexopoulou I, Vassilikogiannakis G. Angew. Chem. Int. Ed. 2012; 51: 8868
• 9c For fluorenone, see: Xia J.-B, Zhu C, Chen C. J. Am. Chem. Soc. 2013; 135: 17494
• 9d For methylene blue, see: Pitre SP, McTiernan CD, Ismaili H, Scaiano JC. ACS Catal. 2014; 4: 2530
• 9e For atropisomeric thiourea derivatives, see: Vallavoju N, Selvakumar S, Jockusch S, Sibi MP, Sivaguru J. Angew. Chem. Int. Ed. 2014; 53: 5604

For some examples of PIET from S ₁, see:
• 10a Ohkubo K, Kobayashi T, Fukuzumu S. Angew. Chem. Int. Ed. 2011; 50: 8652
• 10b Park JH, Ko KC, Kim E, Park N, Ko JH, Ryu DH, Ahn TK, Lee JY, Son SU. Org. Lett. 2012; 14: 5502
• 11a Montalti M, Credi A, Prodi L, Gandolfi MT. Handbook of Photochemistry . CRC; Boca Raton: 2006. 3rd ed
• 11b Photophysical properties of eosin Y and rhodamine B are shown in Table S1 in Supporting Information.

Rhodamine B was tested as one of the organic dyes. See:
• 12a Neumann M, Füldner S, König B, Zeitler K. Angew. Chem. Int. Ed. 2011; 50: 951
• 12b Pan Y, Kee CW, Chen L, Tan C.-H. Green. Chem. 2011; 13: 2682

For reviews on perfluoroalkyl radicals, see:
• 13a Studer A. Angew. Chem. Int. Ed. 2012; 51: 8950
• 13b Amatov T, Jahn U. Angew. Chem. Int. Ed. 2011; 50: 4542
• 13c Dolbier WR. Jr. Chem. Rev. 1996; 96: 1557

Perfluoroalkyl radical reaction using photocatalysts, see:
• 14a Iqbal N, Jung J, Park S, Cho EJ. Angew. Chem. Int. Ed. 2014; 53: 539
• 14b Oh SH, Malpani YR, Ha N, Jung Y.-S, Han SB. Org. Lett. 2014; 16: 1310
• 14c Carboni A, Dagousset G, Magnier E, Masson G. Org. Lett. 2014; 16: 1240
• 14d Yasu Y, Arai Y, Tomita R, Koike T, Akita M. Org. Lett. 2014; 16: 780
• 14e Xu P, Abdukader A, Hu K, Cheng Y, Zhu C. Chem. Commun. 2014; 50: 2308
• 14f Mizuta S, Verhoog S, Engle KM, Khotavivattana T, O’Duill M, Wheelhouse K, Rassias G, Médebielle M, Gouverneur V. J. Am. Chem. Soc. 2013; 135: 2505
• 14g Yoshioka E, Kohtani S, Tanaka E, Miyabe H. Synlett 2013; 24: 1578
• 14h Ye Y, Sanford MS. J. Am. Chem. Soc. 2012; 134: 9034
• 14i Yasu Y, Koike T, Akita M. Angew. Chem. Int. Ed. 2012; 51: 9567
• 14j Nagib DA, MacMillan DW. C. Nature (London, U.K.) 2011; 480: 224
• 14k Pham PV, Nagib DA, MacMillan DW. C. Angew. Chem. Int. Ed. 2011; 50: 6119

For selected recent studies on perfluoroalkyl radical reaction, see:
• 15a Yang F, Klumphu P, Liang Y.-M, Lipshutz BH. Chem. Commun. 2014; 50: 936
• 15b Li L, Deng M, Zheng S.-C, Xiong Y.-P, Tan B, Liu X.-Y. Org. Lett. 2014; 16: 504
• 15c Zhu R, Buchwald SL. Angew. Chem. Int. Ed. 2013; 52: 12655
• 15d Zhang B, Mück-Lichtenfeld C, Daniliuc CG, Studer A. Angew. Chem. Int. Ed. 2013; 52: 10792
• 15e Deb A, Manna S, Modak A, Patra T, Maity S, Maiti D. Angew. Chem. Int. Ed. 2013; 52: 9747
• 15f Seo S, Taylor JB, Greaney MF. Chem. Commun. 2013; 49: 6385
• 15g Yang Y.-D, Iwamoto K, Tokunaga E, Shibata N. Chem. Commun. 2013; 49: 5510
• 15h Hafner A, Bihlmeier A, Nieger M, Klopper W, Bräse S. J. Org. Chem. 2013; 78: 7938
• 15i Li Z, Cui Z, Liu Z.-Q. Org. Lett. 2013; 15: 406
• 15j Herrmann AT, Smith LL, Zakarian A. J. Am. Chem. Soc. 2012; 134: 6976
• 15k Zeng R, Fu C, Ma S. Angew. Chem. Int. Ed. 2012; 51: 3888
• 15l Mejía E, Togni A. ACS Catal. 2012; 2: 521
• 15m Yoshioka E, Kohtani S, Sawai K, Kentefu Tanaka E, Miyabe H. J. Org. Chem. 2012; 77: 8588
• 15n Wang X, Ye Y, Zhang S, Feng J, Xu Y, Zhang Y, Wang J. J. Am. Chem. Soc. 2011; 133: 16410
• 15o Zhang C.-P, Wang Z.-L, Chen Q.-Y, Zhang C.-T, Gu Y.-C, Xiao J.-C. Chem. Commun. 2011; 47: 6632
• 15p Tonoi T, Nishikawa A, Yajima T, Nagano H, Mikami K. Eur. J. Org. Chem. 2008; 1331
• 15q Yajima T, Nagano H. Org. Lett. 2007; 9: 2513
• 15r Itoh Y, Mikami K. Org. Lett. 2005; 7: 4883

Our studied on the radical reactions:
• 16a Miyabe H, Takemoto Y. Universal Org. Chem. 2013; 2: 1 ; http://www.hoajonline.com/orgchem/2053-7670/2/1
• 16b Miyabe H. Synlett 2012; 23: 1709
• 17 General Procedure: A suspension of substrate in H₂O (10 mL) was degassed using three pump–thaw cycles under argon atmosphere at 0 °C. To this suspension were added (i-Pr)₂NEt (192 μL, 1.10 mmol), rhodamine B (24 mg, 0.050 mmol), and i-C₃F₇I (705 μL, 5.00 mmol) at r.t. The stirring reaction mixture was irradiated with white LED lamp (1000 lm) at r.t. After 0.5–1 h, the reaction mixture was concentrated under reduced pressure. Rough purification of the residue by flash silica gel column chromatography afforded the products as a mixture of isomers. The ratio of products was determined by ¹H NMR analysis of the mixture. Second purification of the mixture by flash silica gel column chromatography or preparative TLC afforded the isolated isomers. 1-Methoxy-4-[6,7,7,7-tetrafluoro-4-iodo-6-(trifluoromethyl)hepat-1-yl]benzene (2): Colorless oil. IR (KBr): 2937, 2837, 1612, 1513, 1462 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 7.09 (2 H, br dt, J = 8.7, 2.5 Hz), 6.84 (2 H, br dt, J = 8.7, 2.5 Hz), 4.36–4.30 (1 H, m), 3.79 (3 H, s), 2.96–2.75 (2 H, m), 2.67–2.51 (2 H, m), 1.87–1.66 (4 H, m). ¹³C NMR (101 MHz, CDCl₃): δ = 157.9, 133.4, 129.2, 120.7 (qd, J = 288, 28 Hz), 120.4 (qd, J = 288, 29 Hz), 113.8, 91.9 (dsept, J = 210, 32 Hz), 55.2, 40.3 (d, J = 2 Hz), 39.6 (d, J = 18 Hz), 33.7, 31.6, 22.3. ¹⁹F NMR (376 MHz, CDCl₃): δ = –76.5 (3 F, quin, J = 9 Hz), –7.8 (3 F, br quin, J = 9 Hz), –186.1 (1 F, m). HRMS (ESI⁺): m/z calcd for C₁₅H₁₆F₇IONa [M + Na⁺]: 495.0026; found: 495.0042.
• 18 Mchedlov-Petrossyan NO, Kukhtik VI, Bezugliy VD. J. Phys. Org. Chem. 2003; 16: 380
• 19 Arbeloa IL, Rohatgi-Mukherjee KK. Chem. Phys. Lett. 1986; 129: 607
• 20 Oxidation potential of rhodamine B in S ₁ (RhB⁺/RhB^*) is roughly estimated by subtracting E ₀₀ ¹ (S0–S1 transition energy, 2.2 eV)¹¹ from oxidation potential in S ₀ [RhB⁺/RhB, +0.92 V vs. SCE in H₂O (pH = 7.5)]: E _ox* (RhB⁺/RhB^*) = E _ox (RhB⁺/RhB) – E ₀₀ ¹ = +0.92 (V) – 2.2 (V) = –1.3 V vs. SCE. See: Jiao K, Li Q, Sun W, Wang Z. Chem. Res. Chin. Univ. 2005; 21: 145
• 21a Rozhkov IN, Igumnov SM, Bekker GY, Pletnev SI, Rempel GD, Deev LE. Bull. Acad. Sci. USSR, Div. Chem. Sci. 1990; 38: 2041
• 21b Rozhkov IN, Igumnov SM, Bekker GY, Pletnev SI, Rempel GD, Deev LE. Izv. Akad. Nauk SSSR, Ser. Khim. 1989; 10: 2222
• 22a Beckwith AL. J. Tetrahedron 1981; 37: 3073
• 22b Spellmeyer DC, Houk KN. J. Org. Chem. 1987; 52: 959