LETTER
Iodination of Arylboronic Acids and Biaryl Synthesis
999
aryls 3 were obtained in good to excellent yields.15 The
method exhibited wide tolerance of functional groups in-
cluding ether (Table 3, entries 2–7, 10 and 22), carbon–chlo-
rine bonds (Table 3, entries 7–10 and 16), aldehyde (Table
1995, 60, 7508. (c) Murata, M.; Watanabe, S.; Masuda, Y.
J. Org. Chem. 1997, 62, 6458. (d) Murata, M.; Oyama, T.;
Watanabe, S.; Masuda, Y. J. Org. Chem. 2000, 65, 164.
(
e) Kleeberg, C.; Dang, L.; Lin, Z.; Marder, T. B. Angew.
Chem. Int. Ed. 2009, 48, 5350. (f) Shimada, S.; Batsanov, A.
S.; Howard, J. A. K.; Marder, T. B. Angew. Chem. Int. Ed.
3, entries 11 and 12), ester (Table 3, entries 13–16), cyano
(Table 3, entry 17), naphthalene (Table 3, entries 18–20),
2
001, 40, 2168.
carbon–fluorine bonds (Table 3, entry 19), acetyl (Table 3,
entry 20), and O-heterocyclic (Table 3, entries 21 and 22) on
the arylboronic acid.
(6) For the direct borylation of arenes via C–H bond activation,
see: (a) Cho, J.-Y.; Iverson, C. N.; Smith, M. R. III. J. Am.
Chem. Soc. 2000, 122, 12868. (b) Cho, J.-Y.; Tse, M. K.;
Holmes, D.; Maleczka, R. E. Jr.; Smith, M. R. III. Science
In summary, we have developed a simple, general and ef-
ficient method for the metal-free iodination of arylboronic
acids with iodine in the presence of potassium carbonate
as the base. The method is highly tolerant toward various
functional groups present in the substrates. Importantly,
the iodination strategy could also be applied efficiently to
the one-pot synthesis of biaryl derivatives. These conve-
nient and practical methods should attract attention from
industrial and academic research.
2
002, 295, 305. (c) Ishiyama, T.; Takagi, J.; Ishida, K.;
Miyaura, N. J. Am. Chem. Soc. 2002, 124, 390. (d) Boller, T.
M.; Murphy, J. M.; Hapke, M.; Ishiyama, T.; Miyaura, N.;
Hartwig, J. F. J. Am. Chem. Soc. 2005, 127, 14263.
(e) Mkhalid, I. A. I.; Conventry, D. N.; Albesa-Jove, D.;
Batsanov, A. S.; Howard, J. A. K.; Perutz, R. N.; Marder, T.
B. Angew. Chem. Int. Ed. 2006, 45, 489. (f) Boebel, T. A.;
Hartwig, J. F. J. Am. Chem. Soc. 2008, 130, 7534.
(
g) Kawamorita, S.; Ohmiya, H.; Hara, K.; Fukuoka, A.;
Sawamura, M. J. Am. Chem. Soc. 2009, 131, 5058.
h) Mkhalid, I. A. I.; Barnard, J. H.; Marder, T. B.; Murphy,
(
J. M.; Hartwig, J. F. Chem. Rev. 2010, 110, 890; and
references cited therein.
Acknowledgment
(
(
7) Organotrifluoroborates: (a) Molander, G. A.; Ellis, N. Acc.
Chem. Res. 2007, 40, 275. (b) Darses, S.; Genet, J.-P. Chem.
Rev. 2008, 108, 288.
8) (a) Yang, H.; Li, Y.; Jiang, M.; Wang, J.; Fu, H. Chem. Eur.
J. 2011, 17, 5652. (b) Zhang, G.; Lv, G.; Li, L.; Chen, F.;
Cheng, J. Tetrahedron Lett. 2011, 52, 1993. (c) Ren, Y.-L.;
Tian, X.-Z.; Dong, C.; Zhao, S.; Wang, J.; Yan, M.; Qi, X.;
Liu, G. Catal. Commun. 2011, 32, 15. (d) Thiebes, C.;
Prakash, G. K. S.; Petasis, N. A.; Olah, G. A. Synlett 1998,
The authors wish to thank the National Natural Science Foundation
of China (Grant Nos. 21172128, 21372139, 21105054 and
21221062), and the Ministry of Science and Technology of China
(Grant No. 2012CB722605) for financial support.
Supporting Information for this article is available online at
http://www.thieme-connect.com/ejournals/toc/synlett.SnoIufproig
m
iotSrat
n
ungIifoop
r
t
1
41. (e) Kabalka, G. W.; Sastry, K. A. R.; Sastry, U.;
References and Notes
Somayaji, V. Org. Prep. Proced. Int. 1982, 14, 359.
9) (a) 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. (b) Gooßen, L. J.; Deng, G.; Levy, L. M.
Science 2006, 313, 662. (c) Horton, D. A.; Bourne, G. T.;
Smythe, M. L. Chem. Rev. 2003, 103, 893. (d) Hajduk, P. J.;
Bures, M.; Praestgaard, J.; Fesik, S. W. J. Med. Chem. 2000,
(
(1) For selected papers, see: (a) Tian, J.-S.; Ng, K. W. J.; Wong,
J.-R.; Loh, T.-P. Angew. Chem. Int. Ed. 2012, 51, 9105.
(b) Donohoe, T. J.; Kabeshov, M. A.; Rathi, A. H.; Smith, I.
E. D. Org. Biomol. Chem. 2012, 10, 1093. (c) Yan, Y.;
Wang, Z. Chem. Commun. 2011, 47, 9513. (d) Wan, C.;
Gao, L.; Wang, Q.; Zhang, J.; Wang, Z. Org. Lett. 2010, 12,
3
902. (e) Yan, Y.; Zhang, Y.; Feng, C.; Zha, Z.; Wang, Z.
Angew. Chem. Int. Ed. 2012, 51, 8077. For a recent review,
see: (f) Finkbeiner, P.; Nachtsheim, B. J. Synthesis 2013, 45,
4
3, 3443. (e) 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. (f) Partridge, B. M.; Hartwig, J.
F. Org. Lett. 2013, 15, 140.
979; and references therein.
(
(
(
2) Metal-Catalyzed Cross-Coupling Reactions; Diederich, F.;
Stang, P. J., Eds.; Wiley-VCH: Weinheim, 1997.
3) March, J. Advanced Organic Chemistry; Wiley-
Interscience: New York, 2000, 4th ed..
4) For selected papers, see: (a) Wirth, H. O.; Konigstein, O.;
Kern, W. Liebigs Ann. Chem. 1977, 42, 4049. (b) Ahmed, S.;
Razaq, S. Tetrahedron 1976, 32, 503. (c) Suzuki, H.;
Nakamura, K.; Goto, R. Bull. Chem. Soc. Jpn. 1966, 39, 128.
(
10) (a) Markham, A.; Goa, K. L. Drugs 1997, 54, 299.
b) Croom, K. F.; Keating, G. M. Am. J. Cardiovasc. Drugs
004, 4, 395.
(
2
(
(
(
11) Matheron, M. E.; Porchas, M. Plant Dis. 2004, 88, 665.
12) Poetsch, E. Kontakte 1988, 15.
13) K CO (99.997%) was purchased from Alfa Aesar and
2
3
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).
(
(
d) Suzuki, H. Bull. Chem. Soc. Jpn. 1970, 43, 481.
e) Shimizu, A.; Yamataka, K.; Isoya, T. Bull. Chem. Soc.
Jpn. 1985, 58, 1611. (f) Lulinski, P.; Skulski, L. Bull. Chem.
Soc. Jpn. 1997, 70, 1665. (g) Krassowska-Swiebocka, B.;
Lulinski, P.; Skulski, L. Synthesis 1995, 926. (h) Bachki, A.;
Foabelo, F.; Yus, M. Tetrahedron 1994, 50, 5139.
(
14) Aryl Iodides (2); General Procedure
Arylboronic acid 1 (0.5 mmol) and K CO (1 mmol, 138.0
2
3
(
i) Castanet, A.-S.; Colobert, F.; Broutin, P.-E. Tetrahedron
mg) were added to a 20 mL Schlenk-tube equipped with a
magnetic stir bar. The tube was evacuated twice and back-
filled with N . MeCN (2 mL) and I (0.75 mmol, 191 mg)
Lett. 2002, 43, 5047. (j) Sy, W.-W.; Lodge, B. A.; By, A. W.
Synth. Commun. 1990, 20, 877.
2
2
(
5) For selected transition-metal-catalyzed borylation reactions,
see: (a) Hall, D. G. Boronic Acids: Preparation,
Applications in Organic Synthesis and Medicine; Wiley-
VCH: Weinheim, 2011, and references cited therein.
were added to the tube at r.t. under a stream of N , and the
2
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 H O
2
(
10 mL) was added. The aq layer was extracted with EtOAc
(
b) Ishiyama, T.; Murata, M.; Miyaura, N. J. Org. Chem.
©
Georg Thieme Verlag Stuttgart · New York
Synlett 2014, 25, 995–1000