Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml
Synlett 2014; 25(07): 995-1000
DOI: 10.1055/s-0033-1340871
DOI: 10.1055/s-0033-1340871
letter
Metal-Free Iodination of Arylboronic Acids and the Synthesis of Biaryl Derivatives
Further Information
Publication History
Received: 25 December 2013
Accepted after revision: 05 February 2014
Publication Date:
14 March 2014 (online)
Abstract
A simple, general and efficient method is developed for the metal-free iodination of arylboronic acids. The protocol uses very cheap molecular iodine as the halide source and potassium carbonate as the base. The method is highly tolerant of various functional groups present in the substrates. Importantly, the iodination strategy can also be applied very effectively in the one-pot, two-step synthesis of biaryl derivatives.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
- Supporting Information
-
References and Notes
- 1a Tian J.-S, Ng KW. J, Wong J.-R, Loh T.-P. Angew. Chem. Int. Ed. 2012; 51: 9105
- 1b Donohoe TJ, Kabeshov MA, Rathi AH, Smith IE. D. Org. Biomol. Chem. 2012; 10: 1093
- 1c Yan Y, Wang Z. Chem. Commun. 2011; 47: 9513
- 1d Wan C, Gao L, Wang Q, Zhang J, Wang Z. Org. Lett. 2010; 12: 3902
- 1e Yan Y, Zhang Y, Feng C, Zha Z, Wang Z. Angew. Chem. Int. Ed. 2012; 51: 8077
- 1f Finkbeiner P, Nachtsheim BJ. Synthesis 2013; 45: 979 ; and references therein
- 2 Metal-Catalyzed Cross-Coupling Reactions . Diederich F, Stang PJ. Wiley-VCH; Weinheim: 1997
- 3 March J. Advanced Organic Chemistry . Wiley-Interscience; New York: 2000. 4th ed.
- 4a Wirth HO, Konigstein O, Kern W. Liebigs Ann. Chem. 1977; 42: 4049
- 4b Ahmed S, Razaq S. Tetrahedron 1976; 32: 503
- 4c Suzuki H, Nakamura K, Goto R. Bull. Chem. Soc. Jpn. 1966; 39: 128
- 4d Suzuki H. Bull. Chem. Soc. Jpn. 1970; 43: 481
- 4e Shimizu A, Yamataka K, Isoya T. Bull. Chem. Soc. Jpn. 1985; 58: 1611
- 4f Lulinski P, Skulski L. Bull. Chem. Soc. Jpn. 1997; 70: 1665
- 4g Krassowska-Swiebocka B, Lulinski P, Skulski L. Synthesis 1995; 926
- 4h Bachki A, Foabelo F, Yus M. Tetrahedron 1994; 50: 5139
- 4i Castanet A.-S, Colobert F, Broutin P.-E. Tetrahedron Lett. 2002; 43: 5047
- 4j Sy W.-W, Lodge BA, By AW. Synth. Commun. 1990; 20: 877
- 5a Hall DG. Boronic Acids: Preparation, Applications in Organic Synthesis and Medicine. Wiley-VCH; Weinheim: 2011. ; and references cited therein
- 5b Ishiyama T, Murata M, Miyaura N. J. Org. Chem. 1995; 60: 7508
- 5c Murata M, Watanabe S, Masuda Y. J. Org. Chem. 1997; 62: 6458
- 5d Murata M, Oyama T, Watanabe S, Masuda Y. J. Org. Chem. 2000; 65: 164
- 5e Kleeberg C, Dang L, Lin Z, Marder TB. Angew. Chem. Int. Ed. 2009; 48: 5350
- 5f Shimada S, Batsanov AS, Howard JA. K, Marder TB. Angew. Chem. Int. Ed. 2001; 40: 2168
- 6a Cho J.-Y, Iverson CN, Smith MR. III. J. Am. Chem. Soc. 2000; 122: 12868
- 6b Cho J.-Y, Tse MK, Holmes D, Maleczka RE. Jr, Smith MR. III. Science 2002; 295: 305
- 6c Ishiyama T, Takagi J, Ishida K, Miyaura N. J. Am. Chem. Soc. 2002; 124: 390
- 6d Boller TM, Murphy JM, Hapke M, Ishiyama T, Miyaura N, Hartwig JF. J. Am. Chem. Soc. 2005; 127: 14263
- 6e Mkhalid IA. I, Conventry DN, Albesa-Jove D, Batsanov AS, Howard JA. K, Perutz RN, Marder TB. Angew. Chem. Int. Ed. 2006; 45: 489
- 6f Boebel TA, Hartwig JF. J. Am. Chem. Soc. 2008; 130: 7534
- 6g Kawamorita S, Ohmiya H, Hara K, Fukuoka A, Sawamura M. J. Am. Chem. Soc. 2009; 131: 5058
- 6h Mkhalid IA. I, Barnard JH, Marder TB, Murphy JM, Hartwig JF. Chem. Rev. 2010; 110: 890 ; and references cited therein
- 7a Molander GA, Ellis N. Acc. Chem. Res. 2007; 40: 275
- 7b Darses S, Genet J.-P. Chem. Rev. 2008; 108: 288
- 8a Yang H, Li Y, Jiang M, Wang J, Fu H. Chem. Eur. J. 2011; 17: 5652
- 8b Zhang G, Lv G, Li L, Chen F, Cheng J. Tetrahedron Lett. 2011; 52: 1993
- 8c Ren Y.-L, Tian X.-Z, Dong C, Zhao S, Wang J, Yan M, Qi X, Liu G. Catal. Commun. 2011; 32: 15
- 8d Thiebes C, Prakash GK. S, Petasis NA, Olah GA. Synlett 1998; 141
- 8e Kabalka GW, Sastry KA. R, Sastry U, Somayaji V. Org. Prep. Proced. Int. 1982; 14: 359
- 9a Bringmann G, Günther C, Ochse M, Schupp O, Tasler S. Biaryls in Nature: A Multi-Faceted Class of Stereochemically, Biosynthetically, and Pharmacologically Intriguing Secondary Metabolites. Springer-Verlag; New York: 2001
- 9b Gooßen LJ, Deng G, Levy LM. Science 2006; 313: 662
- 9c Horton DA, Bourne GT, Smythe ML. Chem. Rev. 2003; 103: 893
- 9d Hajduk PJ, Bures M, Praestgaard J, Fesik SW. J. Med. Chem. 2000; 43: 3443
- 9e Sun C.-L, Li H, Yu D.-G, Yu M, Zhou X, Lu X.-Y, Huang K, Zheng S.-F, Li B.-J, Shi Z.-J. Nat. Chem. 2010; 2: 1044
- 9f Partridge BM, Hartwig JF. Org. Lett. 2013; 15: 140
- 10a Markham A, Goa KL. Drugs 1997; 54: 299
- 10b Croom KF, Keating GM. Am. J. Cardiovasc. Drugs 2004; 4: 395
- 11 Matheron ME, Porchas M. Plant Dis. 2004; 88: 665
- 12 Poetsch E. Kontakte 1988; 15
- 13 K2CO3 (99.997%) was purchased from Alfa Aesar and contains Si (1 ppm), Ca (2 ppm) and Na (4 ppm); other elements including: Al, Bi, Cr, Fe, Mn, Sr, V, Sb, B, Co, Pb, Mo, Te, Zn, As, Cd, Cu, Li, Ni, Ag, Sn, Zr, Ba, In, Mg, P and Ti were not detected by ICP/AA (data provided by Alfa Aesar).
- 14 Aryl Iodides (2); General Procedure Arylboronic acid 1 (0.5 mmol) and K2CO3 (1 mmol, 138.0 mg) were added to a 20 mL Schlenk-tube equipped with a magnetic stir bar. The tube was evacuated twice and back-filled with N2. MeCN (2 mL) and I2 (0.75 mmol, 191 mg) were added to the tube at r.t. under a stream of N2, and the tube was sealed and placed into a pre-heated oil bath at 80 °C for 8–12 h. The resulting solution was cooled to r.t. and H2O (10 mL) was added. The aq layer was extracted with EtOAc (3 × 5 mL). For products 2s and 2t, HCl (1 M) was added to the aq solution until pH 2 before extraction. The combined organic phase was dried over anhydrous Na2SO4, filtered and concentrated by rotary evaporation. Purification of the residue by column chromatography on silica gel provided the desired product 2a–v. Data for three representative examples are provided. PE = petroleum ether. 1-Iodo-4-methoxybenzene (2g) [16] Eluent: PE; yield: 93.6 mg (80%); white solid; mp 49–50 °C. 1H NMR (300 MHz, CDCl3): δ = 7.54 (d, J = 8.9 Hz, 2 H), 6.68 (d, J = 8.9 Hz, 2 H), 3.77 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 159.6, 138.3, 116.5, 82.8, 55.4. EI-MS: m/z [M]+ = 234.0. 1-Chloro-3-iodobenzene (2k) [17] Eluent: PE; yield: 86.8 mg (73%); yellow oil. 1H NMR (300 MHz, CDCl3): δ = 7.75 (s, 1 H), 7.60 (d, J = 7.9 Hz, 1 H), 7.33 (d, J = 7.9 Hz, 1 H), 7.02 (t, J = 7.9 Hz, 1 H). 13C NMR (75 MHz, CDCl3): δ = 137.3, 135.8, 135.2, 131.1, 128.1, 94.3. EI-MS: m/z [M]+ = 237.9. 1-Iododibenzo[b,d]furan (2v) [8a] Eluent: PE–EtOAc, 20:1; yield: 129.4 mg (88%); white solid; mp 48–49 °C. 1H NMR (300 MHz, CDCl3): δ = 7.90–7.77 (m, 3 H), 7.65 (d, J = 7.9 Hz, 1 H), 7.47 (d, J = 6.9 Hz, 1 H), 7.37 (d, J = 6.9 Hz, 1 H), 7.08 (t, J = 7.9 Hz, 1 H). 13C NMR (75 MHz, CDCl3): δ = 156.5, 155.7, 136.0, 127.8, 124.6, 124.5, 124.4, 123.3, 121.3, 120.6, 112.2, 75.6. EI-MS: m/z [M]+ = 294.0.
- 15 Biaryls (3); General Procedure Arylboronic acid 1 (0.5 mmol) and K2CO3 (1 mmol, 138.0 mg) were added to a 20 mL Schlenk-tube equipped with a magnetic stir bar. The tube was evacuated twice and back-filled with N2. MeCN (2 mL) and I2 (0.75 mmol, 191 mg) were added to the tube at r.t. under a stream of N2, and the tube was sealed and placed into a pre-heated oil bath at 80 °C for 8–12 h. The resulting solution was cooled to r.t., and then arylboronic acid 1′ (0.75 mmol) and Pd(OAc)2 (0.025 mmol, 5.6 mg) were added, and the mixture stirred at 80 °C for 12–16 h. The resulting solution was cooled to r.t. and H2O (10 mL) was added. The aq layer was extracted with EtOAc (3 × 5 mL). The combined organic phase was dried over anhydrous Na2SO4, filtered and concentrated by rotary evaporation, and the residue was purified by column chromatography on silica gel to provide the desired product 3a–v. Data for three representative examples are provided. 3-Methoxy-1,1′-biphenyl (3c) Eluent: PE–EtOAc, 100:1; yield: 70.8 mg (77%); yellow oil. 1H NMR (400 MHz, CDCl3): δ = 7.63 (d, J = 6.9 Hz, 2 H), 7.47 (t, J = 7.3 Hz, 2 H), 7.41–7.37 (m, 2 H), 7.22 (d, = 8.2 Hz, 1 H), 7.17 (s, 1 H), 6.94 (d, J = 8.2 Hz, 1 H), 3.89 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 160.1, 142.9, 141.2, 129.9, 128.9, 127.5, 127.3, 119.8, 113.0, 112.8, 55.4. EI-MS: m/z [M]+ = 184.1. Methyl 4′-Methyl-[1,1′-biphenyl]-4-carboxylate (3n) Eluent: PE–EtOAc, 100:1; yield: 98.4 mg (87%); white solid; mp 102–103 °C. 1H NMR (400 MHz, CDCl3): δ = 8.09 (d, J = 8.7 Hz, 2 H), 7.64 (d, J = 8.2 Hz, 2 H), 7.52 (d, J = 8.2 Hz, 2 H), 7.27 (d, J = 8.7 Hz, 2 H), 3.93 (s, 3 H), 2.40 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 167.1, 145.7, 138.2, 137.2, 130.2, 129.7, 128.7, 127.2, 126.9, 52.2, 21.2. EI-MS: m/z [M]+ = 226.1. 3′-Methyl-[1,1′-biphenyl]-4-carbonitrile (3q) Eluent: PE–EtOAc, 100:1; yield: 78.2 mg (81%); colorless oil. 1H NMR (400 MHz, CDCl3): δ = 7.71 (d, J = 8.2 Hz, 2 H), 7.67 (d, J = 8.2 Hz, 2 H), 7.39–7.36 (m, 3 H), 7.23 (d, J = 6.0 Hz, 1 H), 2.43 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 145.9, 139.3, 138.9, 132.6, 129.5, 129.1, 128.1, 127.8, 124.5, 119.1, 110.9, 21.6. EI-MS: m/z [M]+ = 193.1.
- 16 George WK, Arjun RM. Tetrahedron Lett. 2004; 45: 343
- 17 Yang SH, Li CS, Cheng CH. J. Org. Chem. 1987; 52: 691
For selected papers, see:
For a recent review, see:
For selected papers, see:
For selected transition-metal-catalyzed borylation reactions, see:
For the direct borylation of arenes via C–H bond activation, see:
Organotrifluoroborates: