pubs.acs.org/joc
various naturally occurring compounds,1 such as alcyopter-
Efficient Synthesis of 3-Arylphthalides using
Palladium-Catalyzed Arylation of Aldehydes with
Organoboronic Acids
osin E,2a cytosporone E,2b fuscinarin,2c rubiginone H,3a iso-
pestacin,3b and cryphonectric acid.3c Especially, 3-arylphthalides
(5) Selected recent examples of noncatalytic synthesis for 3-arylphthalides:
(a) Hayat, S.; Atta-ur-Rahman; Choudhary, M. I.; Khan, K. M.; Bayer, E.
Tetrahedron Lett. 2001, 42, 1647–1649. (b) Garibay, P.; Vesø, P.; Begtrup, M.;
Hoeg-Jensen, T. J. Comb. Chem. 2001, 3, 332–340. (c) Yus, M.; Foubelo, F.;
ꢀ
Ferrandez, J. V. Tetrahedron 2003, 59, 2083–2092. (d) Mahmoodi, N. O.;
Salehpour, M. J. Heterocycl. Chem 2003, 40, 875–878. (e) Knepper, K.; Ziegert,
Masami Kuriyama,*,† Natsuki Ishiyama,†
Rumiko Shimazawa,‡ Ryuichi Shirai,‡ and
Osamu Onomura*,†
†Graduate School of Biomedical Sciences, Nagasaki
University, 1-14 Bunkyo-machi, Nagasaki 852-8521, Japan,
€
R. E.; Brase, S. Tetrahedron 2004, 60, 8591–8603. (f) Pahari, P.; Senapati, B.;
Mal, D. Tetrahedron Lett. 2004, 45, 5109–5112. (g) Pedrosa, R.; Sayalero, S.;
Vicente, M. Tetrahedron 2006, 62, 10400–10407. (h) Karnik, A. V.; Kamath, S. S.
Synthesis 2008, 1832–1834.
‡
and Faculty of Pharmaceutical Sciences, Doshisha Women’s
College of Liberal Arts, Kodo, Kyotanabe, Kyoto 610-0395,
Japan
(6) Recent examples of transition-metal-catalyzed methods: (a) Everaere,
K.; Scheffler, J.-L.; Mortreux, A.; Carpentier, J.-F. Tetrahedron Lett. 2001,
42, 1899–1901. (b) Witulski, B.; Zimmermann, A. Synlett 2002, 1855–1859.
(c) Kawasaki, T.; Saito, S.; Yamamoto, Y. J. Org. Chem. 2002, 67, 2653–
2658. (d) Kosaka, M.; Sekiguchi, S.; Naito, J.; Uemura, M.; Kuwahara, S.;
Watanabe, M.; Harada, N.; Hiroi, K. Chirality 2005, 17, 218–232.
(7) Reviews on transition-metal-catalyzed heterocyclic synthesis: (a)
Transition Metals for Organic Synthesis; Beller, M., Bolm, C., Eds.; Wiley-
VCH Verlag GmbH: Weinheim, 1998. (b) Tsuji, J. Transition Metal Reagents
and Catalysts; John Wiley & Sons Ltd.: New York, 2000. (c) Yet, L. Chem. Rev.
2000, 100, 2963–3007. (d) Nakamura, I.; Yamamoto, Y. Chem. Rev. 2004, 104,
2127–2198. (e) Deiters, A.; Martin, S. F. Chem. Rev. 2004, 104, 2199–2238.
(f) McReynolds, M. D.; Dougherty, J. M.; Hanson, P. R. Chem. Rev. 2004, 104,
2239–2258. (g) Zeni, G.; Larock, R. C. Chem. Rev. 2004, 104, 2285–2309.
(h) Alonso, F.; Beletskaya, I. P.; Yus, M. Chem. Rev. 2004, 104, 3079–3159.
(8) Cr-catalyzed addition of arylzinc reagents to aldehydes: (a) Ogawa,
Y.; Saiga, A.; Mori, M.; Shibata, T.; Takagi, K. J. Org. Chem. 2000, 65,
1031–1036. Ni-catalyzed cyclization of o-halobenzoates with aldehydes:
(b) Rayabarapu, D. K.; Chang, H.-T.; Cheng, C.-H. Chem.;Eur. J. 2004,
10, 2991–2996. Co-catalyzed cyclization of o-halobenzoates with aldehydes:
(c) Chang, H.-T.; Jeganmohan, M.; Cheng, C.-H. Chem.;Eur. J. 2007, 13,
4356–4363. Ni-catalyzed homo-coupling of o-halobenzaldehydes: (d) Chen,
W.-W.; Xu, M.-H.; Lin, G.-Q. Tetrahedron. Lett. 2007, 48, 7508–7511.
(9) (a) Sakai, M.; Ueda, M.; Miyaura, N. Angew. Chem., Int. Ed. 1998, 37,
3279–3281. (b) Ueda, M.; Miyaura, N. J. Org. Chem. 2000, 65, 4450–4452.
(10) Reviews: (a) Fagnou, K.; Lautens, M. Chem. Rev. 2003, 103, 169–
196. (b) Hayashi, T.; Yamasaki, K. Chem. Rev. 2003, 103, 2829–2844.
mkuriyam@nagasaki-u.ac.jp; onomura@nagasaki-u.ac.jp
Received September 12, 2009
The synthesis of 3-arylphthalides via palladium-catalyzed
arylation of aldehydes with organoboronic acids was
achieved using the thioether-imidazolinium carbene li-
gand in good to excellent yields and was carried out using
1.0 mol % of the catalyst with high substrate tolerance.
ꢀ
(c) Miyaura, N. Synlett 2009, 2039–2050. (d) Dıez-Gonzalez, S.; Marion,
N.; Nolan, S. P. Chem. Rev. 2009, 109, 3612–3676.
(11) (a) Suzuki, A. Acc. Chem. Res. 1982, 15, 178–184. (b) Miyaura, N.;
Suzuki, A. Chem. Rev. 1995, 95, 2457–2483. (c) Suzuki, A. J. Organomet.
Chem. 1998, 576, 147–168.
(12) Selected examples of Rh catalyst: (a) Batey, R. A.; Thadani, A. N.;
€
Smil, D. V. Org. Lett. 1999, 1, 1683–1686. (b) Furstner, A.; Krause, H. Adv.
Synth. Catal. 2001, 343, 343–350. (c) Moreau, C.; Hague, C.; Weller, A. S.;
€
Frost, C. G. Tetrahedron Lett. 2001, 42, 6957–6960. (d) Ozdemir, I.; Demir,
Phthalides substituted at C-3 are important heterocycles
possessing interesting biological activities and are found in
S.; C-etinkaya, B. J. Mol. Catal. A: Chem. 2004, 215, 45–48. (e) Imlinger, N.;
Mayr, M.; Wang, D.; Wurst, K.; Buchmeiser, M. R. Adv. Synth. Catal. 2004,
346, 1836–1843. (f) Pucheault, M.; Darses, S.; Genet, J.-P. Chem, Commun.
2005, 4714–4716. (g) Focken, T.; Rudolph, J.; Bolm, C. Synthesis 2005, 429–
436. (h) Son, S. U.; Kim, S. B.; Reingold, J. A.; Carpenter, G. B.; Sweigart, D.
A. J. Am. Chem. Soc. 2005, 127, 12238–12239. (i) Huang, R.; Shaughnessy,
K. H. Chem. Commun 2005, 4484–4486. (j) Imlinger, N.; Wurst, K.;
(1) Lin, G.; Chan, S. S.-K.; Chung, H.-S.; Li, S.-L. Cemistry and
Biological Action of Natural Occurring Phthalides. In Studies in Natural
Products Chemistry; Atta-ur-Rahman, Ed.; Elsevier: Amsterdam, 2005;
Vol. 32, pp 611-669.
(2) 3-Substituted phthalides: (a) Palermo, J. A.; Brasco, M. V. R.;
Spagnuolo, C.; Seldes, A. M. J. Org. Chem. 2000, 65, 4482–4486. (b) Brady,
S. F.; Wagenaar, M. M.; Singh, M. P.; Janso, J. E.; Clardy, J. Org. Lett. 2000,
2, 4043–4046. (c) Yoganathan, K.; Rossant, C.; Ng, S.; Huang, Y.; Butler,
M. S.; Buss, A. D. J. Nat. Prod. 2003, 66, 1116–1117.
(3) 3-Arylphthalides: (a) Puder, C.; Zeeck, A.; Beil, W. J. Antibiot. 2000,
53, 329–336. (b) Strobel, G.; Ford, E.; Worapong, J.; Harper, J. K.; Arif,
A. M.; Grant, D. M.; Fung, P. C. W.; Chau, R. M. W. Phytochemistry 2002,
60, 179–183. (c) Arnone, A.; Assante, G.; Nasini, G.; Strada, S.; Vercesi, A.
J. Nat. Prod. 2002, 65, 48–50.
(4) Examples: (a) Uemura, M.; Take, K.; Hayashi, Y. J. Chem. Soc.,
Chem. Commun. 1983, 858–859. (b) Katsuura, K.; Snieckus, V. Tetrahedron
Lett. 1985, 26, 9–12. (c) Taunton, J.; Wood, J. L.; Schreiber, S. L. J. Am.
Chem. Soc. 1993, 115, 10378–10379. (d) Sartori, G.; Bigi, F.; Tao, X.; Porta,
C.; Maggi, R.; Predieri, G.; Lanfranchi, M.; Pellinghelli, M. A. J. Org. Chem.
1995, 60, 6588–6591. (e) Patil, M. L.; Borate, H. B.; Ponde, D. E.; Bhawal,
B. M.; Deshpande, V. H. Tetrahedron Lett. 1999, 40, 4437–4438. (f) Patil,
M. L.; Borate, H. B.; Ponde, D. E.; Deshpande, V. H. Tetrahedron 2002, 58,
6615–6620.(g) Gonnot, V.; Tisserand, S.; Nicolas, M.; Baati, R.; Mioskowski,
C. Tetrahedron Lett. 2007, 48, 7117–7119. (h) Fei, Z.; McDonald, F. E. Org.
Lett. 2007, 9, 3547–3550.
€
Buchmeiser, M. R. J. Organomet. Chem. 2005, 690, 4433–4440. (k) Ozdemir,
I.; Demir, S.; C-etinkaya, B.; C-etinkaya, E. J. Organomet. Chem. 2005, 690,
5849–5855. (l) Chen, J.; Zhang, X.; Feng, Q.; Luo, M. J. Organomet. Chem.
2006, 691, 470–474. (m) Jagt, R. B. C.; Toullec, P. Y.; De Vries, J. G.;
Feringa, B. L.; Minnaard, A. J. Org. Biomol. Chem. 2006, 4, 773–775.
(n) Duan, H.-F.; Xie, J.-H.; Shi, W.-J.; Zhang, Q.; Zhou, Q.-L. Org. Lett.
2006, 8, 1479–1481. (o) Suzuki, K.; Ishii, S.; Kondo, K.; Aoyama, T. Synlett
2006, 648–650. (p) Suzuki, K.; Kondo, K.; Aoyama, T. Synthesis 2006, 1360–
1364. (q) Yan, C.; Zeng, X.; Zhang, W.; Luo, M. J. Organomet. Chem. 2006,
691, 3391–3396. (r) Arao, T.; Suzuki, K.; Kondo, K.; Aoyama, T. Synthesis
2006, 3809–3814. (s) Jagt, R. B. C.; Toullec, P. Y.; Schudde, E. B.; De Vries,
J. G.; Feringa, B. L.; Minnaard, A. J. J. Comb. Chem. 2007, 9, 407–414.
ꢀ
(t) Gois, P. M. P.; Trindade, A. F.; Veiros, L. F.; Andre, V.; Duarte, M. T.;
Afonso, C. A. M.; Caddick, S.; Cloke, F. G. N. Angew. Chem., Int. Ed. 2007,
€
46, 5750–5753. (u) Noel, T.; Vandyck, K.; Van der Eycken, J. Tetrahedron
2007, 63, 12961–12967. (v) Trindade, A. F.; Gois, P. M. P.; Veiros, L. F.;
ꢀ
Andre, V.; Duarte, M. T.; Afonso, C. A. M.; Caddick, S.; Cloke, F. G.N.
€
€
J. Org. Chem 2008, 73, 4076–4086. (w) Turkmen, H.; Denizalti, S.; Ozdemir,
I.; C-etinkaya, E.; C-etinkaya, B. J. Organomet. Chem. 2008, 693, 425–434.
(x) Xing, C.-H.; Liu, T.-P.; Zheng, J. R.; Ng, J.; Esposito, M.; Hu, Q.-S.
Tetrahedron Lett. 2009, 50, 4953–4957.
9210 J. Org. Chem. 2009, 74, 9210–9213
Published on Web 10/29/2009
DOI: 10.1021/jo901964k
r
2009 American Chemical Society