One-Pot Synthesis of Bisindolylmethanes from Benzyl Alcohols and Indoles Using Catalytic Iodine and Molecular Oxygen under Visible Light Irradiation

Tomoya Nobuta; Akitoshi Fujiya; Norihiro Tada; Tsuyoshi Miura; Akichika Itoh

doi:10.1055/s-0032-1317508

Synlett, Inhaltsverzeichnis

Synlett 2012; 23(20): 2975-2979
DOI: 10.1055/s-0032-1317508

letter

One-Pot Synthesis of Bisindolylmethanes from Benzyl Alcohols and Indoles Using Catalytic Iodine and Molecular Oxygen under Visible Light Irradiation

Tomoya Nobuta

Gifu Pharmaceutical University 1-25-4, Daigaku-nishi, Gifu 501-1196, Japan Fax: +81(58)2308108 eMail: itoha@gifu-pu.ac.jp

,

Akitoshi Fujiya

Gifu Pharmaceutical University 1-25-4, Daigaku-nishi, Gifu 501-1196, Japan Fax: +81(58)2308108 eMail: itoha@gifu-pu.ac.jp

,

Norihiro Tada

Gifu Pharmaceutical University 1-25-4, Daigaku-nishi, Gifu 501-1196, Japan Fax: +81(58)2308108 eMail: itoha@gifu-pu.ac.jp

,

Tsuyoshi Miura

Gifu Pharmaceutical University 1-25-4, Daigaku-nishi, Gifu 501-1196, Japan Fax: +81(58)2308108 eMail: itoha@gifu-pu.ac.jp

,

Akichika Itoh*

Gifu Pharmaceutical University 1-25-4, Daigaku-nishi, Gifu 501-1196, Japan Fax: +81(58)2308108 eMail: itoha@gifu-pu.ac.jp

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

Abstract

Bisindolylmethanes can be directly synthesized from benzyl alcohol and indole in up to 86% yield using molecular oxygen, visible light, and catalytic iodine, which serves as both an oxidant and a Lewis acid.

Key words

photooxidation - iodine - molecular oxygen - bisindolylmethane - benzyl alcohol

Volltext

Referenzen

References and Notes
1 Sundberg RJ. The Chemistry of Indoles . Academic Press; New York: 1970

2a Morris SA, Anderson RJ. Tetrahedron 1990; 46: 715
2b Veluri R, Oka I, Wagner-Döbler I, Laatsch H. J. Nat. Prod. 2003; 66: 1520
2c Garbe TR, Kobayashi M, Shimizu N, Takesue N, Ozawa M, Yukawa H. J. Nat. Prod. 2000; 63: 596

3a Barbero M, Cadamuro S, Dughera S, Magistris C, Venturello P. Org. Biomol. Chem. 2011; 9: 8393
3b Karam A, Alonso JC, Gerganova TI, Ferreira P, Bion N, Barrault J, Jérôme F. Chem. Commun. 2009; 7000
3c Podder S, Choudhury J, Roy UK, Roy S. J. Org. Chem. 2007; 72: 3100
3d Nair V, Abhilash KG, Vidya N. Org. Lett. 2005; 7: 5857
3e Gibbs TJ. K, Tomkinson NC. O. Org. Biomol. Chem. 2005; 3: 4043
3f Liao B.-S, Chen J.-T, Liu S.-T. Synthesis 2007; 3125
3g Yadav JS, Subba Reddy BV, Gayathri KU, Meraj S, Prasad AR. Synthesis 2006; 4121
3h Nair V, Vidya N, Abhilash KG. Synthesis 2006; 3647
3i Zhang Z.-H, Yin L, Wang Y.-M. Synthesis 2005; 1949
3j Ji S.-J, Zhou M.-F, Gu D.-G, Jiang Z.-Q, Loh T.-P. Eur. J. Org. Chem. 2004; 1584
3k Bartoli G, Bosco M, Foglia G, Giuliani A, Marcantoni E, Sambri L. Synthesis 2004; 895
3l Sharma GV. M, Reddy JJ, Lakshmi PS, Krishna PR. Tetrahedron Lett. 2004; 45: 7729
3m Farhanullah Sharon A, Maulik PR, Ram VJ. Tetrahedron Lett. 2004; 45: 5099
3n Mi X, Luo S, He J, Cheng J.-P. Tetrahedron Lett. 2004; 45: 4567
3o Bandgar BP, Shaikh KA. Tetrahedron Lett. 2003; 44: 1959
3p Yadav JS, Reddy BV. S, Murthy CV. S. R, Kumar GM, Madan C. Synthesis 2001; 783

4 Ramachandiran K, Muralidharan D, Perumal PT. Tetrahedron Lett. 2011; 52: 3579
5 Yang J, Wang Z, Pan F, Li Y, Bao W. Org. Biomol. Chem. 2010; 8: 2975
6 Guo X, Pan S, Liu J, Li Z. J. Org. Chem. 2009; 74: 8848

7a Khosropour AR, Mohammadpoor-Baltork I, Khodaei MM, Ghanbary P. Z. Naturforsch. B: Chem. Sci. 2007; 62: 537
7b Whitney S, Grigg R, Derrick A, Keep A. Org. Lett. 2007; 9: 3299

8a Nobuta T, Hirashima S, Tada N, Miura T, Itoh A. Org. Lett. 2011; 13: 2576
8b Kanai N, Nakayama H, Tada N, Itoh A. Org. Lett. 2010; 12: 1948
8c Nobuta T, Hirashima S, Tada N, Miura T, Itoh A. Synlett 2010; 2335
8d Nakayama H, Itoh A. Tetrahedron Lett. 2007; 48: 1131
8e Nakayama H, Itoh A. Chem. Pharm. Bull. 2006; 54: 1620

9 Togo H, Iida S. Synlett 2006; 2159
10 Gao M, Yang Y, Wu Y.-D, Deng C, Shu W.-M, Zhang D.-X, Cao L.-P, She N.-F, Wu A.-X. Org. Lett. 2010; 12: 4026
11 General Procedure: A solution of 4-tert-butylbenzyl alcohol (1a; 0.3 mmol) and I₂ (0.06 mmol) in anhyd EtOAc (5 mL) in a pyrex test tube, purged with an O₂ balloon, was stirred and irradiated externally with four 22-W fluorescent lamps for 20 h. Indole (0.66 mmol) was added, and stirred for 10 min at r.t. The reaction mixture was washed with aq Na₂S₂O₃ and concentrated in vacuo. Purification of the crude product by PTLC (hexane–EtOAc, 4:1) provided 3,3′-bis-(indolyl)-4-tert-butylphenylmethane (3aa; R_f 0.33; yield: 98.1 mg, 86%). 3,3′-Bis(indolyl)-4-tert-butylphenylmethane (3aa): ¹H NMR (400 MHz, CDCl₃): δ = 7.54 (br s, 2 H), 7.36 (d, J = 7.7 Hz, 2 H), 7.26–7.09 (m, 8 H), 6.98–6.94 (m, 2 H), 6.47 (s, 2 H), 5.80 (s, 1 H), 1.27 (s, 9 H). 3,3′-Bis(indolyl)phenylmethane (3ba): ¹H NMR (400 MHz, CDCl₃): δ = 7.44 (br s, 2 H), 7.34–7.08 (m, 11 H), 6.95 (t, J = 7.3 Hz, 2 H), 6.39 (s, 2 H), 5.80 (s, 1 H). 3,3′-Bis(indolyl)-4-methylphenylmethane (3ca): ¹H NMR (400 MHz, CDCl₃): δ = 7.41 (br s, 2 H), 7.34 (d, J = 8.2 Hz, 2 H), 7.17–7.05 (m, 6 H), 7.02 (d, J = 7.7 Hz, 2 H), 6.95 (t, J = 7.2 Hz, 2 H), 6.40 (s, 2 H), 5.78 (s, 1 H), 2.27 (s, 3 H). 3,3′-Bis(indolyl)-4-bromophenylmethane (3da): ¹H NMR (400 MHz, CDCl₃): δ = 7.50 (br s, 2 H), 7.24–7.02 (m, 10 H), 6.89 (m, 2 H), 6.34 (s, 2 H), 5.68 (s, 1 H). 3,3′-Bis(indolyl)-2-naphthylmethane (3ea): ¹H NMR (500 MHz, DMSO-d ₆): δ = 10.90 (br s, 2 H), 7.85–7.73 (m, 4 H), 7.57 (d, J = 8.6 Hz, 1 H), 7.40–7.35 (m, 6 H), 7.04 (t, J = 7.4 Hz, 2 H), 6.91–6.84 (m, 4 H), 6.05 (s, 1 H). 3,3′-Bis(indolyl)-4-chlorophenylmethane (3fa): ¹H NMR (500 MHz, DMSO-d ₆): δ = 10.87 (br s, 2 H), 7.36–6.83 (m, 14 H), 5.85 (s, 1 H). 3,3′-Bis(indolyl)-4-methoxyphenylmethane (3ga): ¹H NMR (500 MHz, CDCl₃): δ = 7.58 (br s, 2 H), 7.35–7.34 (m, 2 H), 7.21–7.09 (m, 6 H), 6.96 (t, J = 7.4 Hz, 2 H), 6.75 (d, J = 8.0 Hz, 2 H), 6.44 (s, 2 H), 5.77 (s, 1 H), 3.70 (s, 3 H). 3,3′-Bis(indolyl)-4-nitrophenylmethane (3ha): ¹H NMR (500 MHz, DMSO-d ₆): δ = 10.92 (br s, 2 H), 8.12 (d, J = 8.6 Hz, 2 H), 7.58 (d, J = 8.6 Hz, 2 H), 7.34 (d, J = 8.0 Hz, 2 H), 7.26 (d, J = 8.0 Hz, 2 H), 7.04–7.01 (m, 2 H), 6.88–6.84 (m, 4 H), 6.00 (s, 1 H). 2,2′-Bis[3-(carboxypropyl)indolyl]-4-methoxyphenylmethane (3gb): ¹H NMR (400 MHz, DMSO-d ₆): δ = 12.00 (br s, 2 H), 10.43 (br s, 2 H), 7.48 (d, J = 7.3 Hz, 2 H), 7.30 (d, J = 7.8 Hz, 2 H), 7.04–6.93 (m, 6 H), 6.87 (d, J = 8.7 Hz, 2 H), 5.97 (s, 1 H), 3.70 (s, 3 H), 2.72–2.69 (m, 4 H), 2.21 (t, J = 7.3 Hz, 4 H), 1.72–1.69 (m, 4 H). 2,2′-Bis[3-(carboxyethyl)indolyl]-4-nitrophenylmethane (3hc): ¹H NMR (500 MHz, DMSO-d ₆): δ = 12.09 (br s, 2 H), 10.78 (br s, 2 H), 8.20 (d, J = 8.6 Hz, 2 H), 7.50 (d, J = 7.4 Hz, 2 H), 7.35 (d, J = 8.6 Hz, 2 H), 7.31 (d, J = 8.0 Hz, 2 H), 7.04 (t, J = 7.4 Hz, 2 H), 6.98–6.95 (m, 2 H), 6.40 (s, 1 H), 3.01–2.88 (m, 4 H), 2.46–2.40 (m, 4 H).Bis(1-methylindol-3-yl)-4-tolylmethane (3cd): 1H NMR (500 MHz, CDCl3): δ = 7.37 (d, J = 8.0 Hz, 2 H), 7.24–7.14 (m, 6 H), 7.05 (d, J = 7.5 Hz, 2 H), 6.97–6.94 (m, 2 H), 6.50 (s, 2 H), 5.83 (s, 1 H), 3.58 (s, 6 H), 2.29 (s, 3 H).�5-(4-Methylphenyl)dipyrromethane (3ce): 1H NMR (500 MHz, CDCl3): δ = 7.91 (br s, 2 H), 7.13–7.09 (m, 4 H), 6.68–6.67 (m, 2 H), 6.16–6.14 (m, 2 H), 5.91 (s, 2 H), 5.43 (s, 1 H), 2.33 (s, 3 H).�