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Organic & Biomolecular Chemistry
DOI: 10.1039/C7OB01237C
ARTICLE
Journal Name
Shao, G. Du, C. Xi, J. Org. Chem. 2016, 81, 6672; (m) Y. Yang,
H. Huang. L. Wu, Y. liang, Org. Bio. Chem. 2014, 12, 5351; (n)
M. Yuan, L. Chen, J. Wang, S. Chen, K. Wang, Y. Xue, G. Yao,
Z. Luo, Y. Zhang, Org. Lett. 2015, 17, 346.
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(a) S. Ghosal, P. H. Rao, D. K. Jaiswal, Y. Kumar, A. W. Frahm,
Phytochemistry 1981, 20, 2003; (b) S. Van Miert, S. Hostyn,
B. U. W. Maes, K. Cimanga, R. Brun, M. Kaiser, P. Mátyus, R.
Dommisse, G. Lemière, A. Vlietinck, L. Pieters, J. Nat. Pro.
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005, 68, 674; (c) C. Schultz, A. Link, M. Leost, Z. W.
Zaharevitz, R. Gussio, E.A. Sausville, L. Meijer, C. Kunick, J.
Med. Chem. 1999, 42, 2909; (d) G. Taraboletti, G. Micheletti,
R. Dossi, P. Borsotti, M. Martinelli, F. Fior-daliso, A J. Ryan, R.
Giavazzi, Clin. Cancer Res. 2005, 11, 2720.
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Typical example see: D.D. Hennings, T. Iwama, V.H. Rawal,
Org. Lett, 1999, 2, 1205
Scheme 8. Proposed reaction mechanism
(a) T. R. Kelly, Q. Li, V. Bhushan, Tetra. Lett. 1990, 31, 161; (b)
W.S. Yue, J. J. Li, Org. Lett. 2002, 4, 2201; (c) R. Grigg, A.
Teasdale, V. Sridharan, Tetra. Lett. 1991, 32, 3859.
E. B. Fleischer, M. Krishnamurthy, S. K. Cheung, J. Am. Chem.
Soc.1975, 97, 3873.
M. G. Banwell, D. W. Lupton, X. Ma, J. Renner, M. O. Sydnes,
Org. Lett. 2004, 6, 2741.
C.C.C.J. Seechurn, M.O. Kitching, T.J. Colacot, V. Snieckus,
Ange. Chem. Int. Ed. 2012, 51, 5062.
(a) J.-M. Bégouin, S. Claudel, C. Gosmini, Synlett. 2009, 2009,
Conclusions
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In conclusion, we have developed a short and useful
synthesis of pharmaceutically important tricyclic biaryl
compounds by direct cross-coupling of 2-halogen benzyl
carbonates and 2-halogen anilines. This methodology has a
wide substrate scope and can be applied to build more
complicated compounds, such as anhydrolycorinone,
isocryptolepine and the CDK kinase inhibitor paullone, in one
step. Our mechanistic study demonstrated that this cascade
reaction proceeded through an intermolecular Miyaura
borylation/selective Suzuki cross-coupling reaction, followed
by intramolecular lactam formation. This direct cross-coupling
method has potential to be applied to other aryl electrophiles,
and currently this part of research is under investigation in our
lab.
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192; (b) J.-M. Begouin, M. Rivard, C. Gosmini, Chem. Comm.
010, 46, 5972; (c) L. K. G. Ackerman, M. M. Lovell, D. J.
Weix, Nature 2015, 524, 454.
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(a) C. E. I. Knappke, S. Grupe, D. Gärtner, M. Corpet, C.
Gosmini, A. J. von Wangelin, A. Chem. Eur. J. 2014, 20, 6828;
(
b) D. A. Everson, D. J. Weix, J. Org. Chem. 2014, 79, 4793-
798.
0 T. Ishiyama, M. Murata, N. Miyaura, J. Org. Chem. 1995, 60,
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7508.
11 The homo-coupling of two aryl electrophiles under similar
reaction condition were reported, see: (a) C. F. Nising, U. K.
Schmid, M. Nieger, S. Bräse, J. Org. Chem. 2004, 69, 6830. (b)
K. L. Billingsley, T. E. Barder, S. L. Buchwald, Angew. Chem.
Int. Ed. 2007, 46, 5359, (c) T. Ishiyama, M. Murata, N.
Miyaura, J. Org. Chem. 1995, 60, 7508.
Acknowledgements
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2 Selected reviews see: (a) J.F. Hartwig, Angew. Chem. Int. Ed.
998, 37, 2046; (b) A.R. Muci, S.L. Buchwald, Topics in Curr.
Chem., 219. 131.
3 J. H. Kirchhoff, M. R. Netherton, I. D. Hills, G. C. Fu. J. Am.
Chem. Soc 2002, 124, 13662.
4 X. Chen, P. Sun, J. Xu, X. Wu, L. Kong, H. Yao, A. Lin, Tetra.
Lett. 2014, 55, 7114.
5 Synthesis of Paullon see: (a) Z. Li, N. Lu, L. Wang, W. Zhang,
Eur. J. Org. Chem. 2012, 1019; (b) D. R. Stuart, P. Alsabeh, M.
Kuhn, K. Fagnou, J. Am. Chem. Soc. 2010, 132, 18326; (c) M.
Tobisu, H. Fujihara, K.Koh, N. Chatani, J. Org. Chem. 2010, 75,
This work was supported by the University Cancer Research
Fund and Eshelman gifted money. The authors thank
Professors Stephen Frye and Qisheng Zhang for comments on
the manuscript, Dr. Jichen Zhao for help with the spectra data
preparation, Professor Crimmins’s lab for assistance on Fourier
transform infrared spectroscopy (FTIR), and Dr. George Dubay
for assistance on HRMS.
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841; (d) T. Opatz, D.Ferenc, Synthesis 2008, 3941; (e) L.
References
Joucla, F. Popowycz, O. Lozach, L. Meijer, B. Joseph,Helv.
Chim. Acta 2007, 90, 753; (f) N. Henry, J. Blu, V. Beneteau,J.-
Y. Merour, Synthesis 2006, 3895. (g) J. B. Bremner, W.
Sengpracha,Tetrahedron 2005, 61, 5489; (h) O. Baudoin, M.
Cesario, D.Guenard, F. Gueritte, J. Org. Chem. 2002, 67,
1
Typical examples of the synthesis of tricyclic biaryls see: (a)
D.E. Ames, A. Opalko. Tetrahedron 1984, 40, 1919; (b) M.A.
Siddiqui, V. Sniekus. Tetra.Lett. 1990, 31, 1523; (c) U. Lauk,
D. Dürst, W. Fischer. Tetra. Lett. 1991, 31, 65; (d) A. I.
Meyers, Hutchings, F. H. Tetra. Lett. 1993, 34, 6185; (e) D.R.
Spring, S. Krishnan, H. E. Blackwell, S. L. Schreiber. J. Am.
Chem. Soc. 2002, 124, 1354; (f) R. Ferraccioli, D. Carenzi, E.
Motti, M. Catellani. J. Am. Chem. Soc. 2006, 128, 722; (g) T.
Furuta, Y. Kitamura, A. Hashimoto, S. Fujii, K. Tanaka, T. Kan,
Org. Lett. 2007, 9, 183; (h) G. W. Wang, T. T. Yuan, D. D. Li,
Angew. Chem. Int. Ed Engl. 2011, 50, 1380; (i) B. S. Bhakuni,
A. Kumar, S. J. Balkrishna, J. A. Sheikh, S. Konar, S. Kumamr,
Org. Lett. 2012, 14, 2838; (j) L. Donati, S. Michel, F. Tillequin,
F-H. Porée. Org. Lett. 2010, 12, 156; (k) V. Rajeshkumar, T.-H.
Lee, S-C. Chuang. Org. Lett. 2013, 15, 1468; (l) S. Wang, P.
1
6 A.-C. Carbonnelle, J. Zhu, Org. Lett. 2000, 2, 3477.
199.
1
1
7 (a) R. Contreras, C. García, T. Mancilla, J. Organomet. Chem.
1
2
983, 246, 213; (b) E. P. Gillis, M. D. Burke, J. Am. Chem. Soc.
007, 129, 6716-6717.
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