Page 3 of 3
ChemComm
Please do not adjust margins
Journal Name
COMMUNICATION
DOI: 10.1039/C5CC08855K
conditions. The substrate scope and functional group tolerance of
this reaction are good and the operation procedure is simple. The
reaction thus constitutes a straightforward access toward 1,1-
diaryl-substituted olefins.12
However, the reaction of diazo compound with arylboronic acid
affords the product with C-C single bond formation, and no olefin
product 3aa could be observed for the reaction of phenylboronic
acid 2a with N-tosylhydrazone 4 (or its sodium salt 5) in the
presence of BQ (eq 2). Control experiments also indicated that 3aa
was not observed when 1,1-diphenylethane 6 was treated with BQ
in dioxane at 100 oC (eq 3). These experiments support the
conclusion that the coupling of diazirine with arylboronic acid
follows a pathway that does not involve diazo intermediate.
The project is supported by National Basic Research Program (973
Program, No. 2012CB821600) and Natural Science Foundation of
China (Grant 21472004 and 21332002).
Notes and references
1
For reviews, see: (a) A. Suzuki, Acc. Chem. Res., 1982, 15, 178; (b) N.
Miyaura and A. Suzuki, Chem. Rev., 1995, 95, 2457; (c) A. Suzuki, In
Metal-Catalyzed Cross-Coupling Reactions; F. Diederich and P. J. Stang,
Eds.; Wiley-VCH: Weinheim, 1998; pp 49-97; (d) N. Miyaura, Top. Curr.
Chem., 2002, 219, 11; (e) N. Miyaura, J. Organomet. Chem., 2002, 653,
54; (f) T. Ishiyama and N. Miyaura, Chem. Rec., 2004, 3, 271; (g) N.
Miyaura, Bull. Chem. Soc. Jpn., 2008, 81, 1535; (h) A. Suzuki, Angew.
Chem. Int. Ed., 2011, 50, 6722.
Scheme 3 A proposed reaction mechanism involving diazo intermediate
2
3
4
For a recent review, see: C.-L. Sun and Z.-J. Shi, Chem. Rev., 2014, 114,
9219.
(2)
For reviews, see: (a) H. Li, Y. Zhang and J. Wang, Synthesis, 2013, 45,
3090; (b) S. Roscales and A. G. Csák,ÿ Chem. Soc. Rev., 2014, 43, 8215.
(a) C. Peng, W. Zhang, G. Yan and J. Wang, Org. Lett., 2009, 11, 1667;
(b) P. K. Elkin, V. V. Levin, A. D. Dilman, M. I. Struchkova, P. A. Belyakov,
D. E. Arkhipov, A. A. Korlyukov and V. A. Tartakovsky, Tetrahedron Lett.,
2011, 52, 5259; (c) G. Wu, Y. Deng, C. Wu, Y. Zhang and J. Wang,
Angew. Chem. Int. Ed., 2014, 53, 10510.
(3)
Thus, an alternative reaction mechanism is proposed as shown in
Scheme 4. The reaction is initiated by nucleophilic attack of the
nitrogen of the diazirine to the boron of arylboronic acid,
generating intermediate A. Subsequently, migration of the aryl
group from boron to the carbon of the three-membered ring
generates intermediate B, with simultaneous ring opening. The
intermediate B is then oxidized with hydrogen shift assisted by BQ
through path a or path b to afford the final product and
hydroquinone, which was detected by GC-MS. Further
investigations are necessary to verify this mechanistic proposal.
5
(a) J. Barluenga, M. Tomás-Gamasa, F. Aznar and C. Valdés, Nat. Chem.,
2009, 1, 494; (b) M. C. Pérez-Aguilar and C. Valdés, Angew. Chem. Int.
Ed., 2012, 51, 5953; (c) D. M. Allwood, D. C. Blakemore, A. D. Brown
and S. V. Ley, J. Org. Chem., 2014, 79, 328.
For a photochemically promoted reaction, see: K. Ito, H. Tamashima, N.
Iwasawa and H. Kusama, J. Am. Chem. Soc., 2011, 133, 3716.
For reviews, see: (a) R. A. Moss, Acc. Chem. Res., 2006, 39, 267 and the
references therein; (b) M. T. H. Liu, Ed. Chemistry of Diazirines; CRC
Press: Boca Raton, Florida, 1987; (c) R. A. Moss, J. Phys. Org. Chem.,
2010, 23, 293.
6
7
8
9
For a review, see: J. Das, Chem. Rev., 2011, 111, 4405.
For selected reports, see: (a) T. Mayer and M. E. Maier, Eur. J. Org.
Chem., 2007, 4711; (b) N. S. Kumar and R. N. Young, Bioorg. Med.
Chem., 2009, 17, 5388; (c) G. Chee, J. C. Yalowich, A. Bodner, X. Wu
and B. B. Hasinoff, Bioorg. Med. Chem., 2010, 18, 830; (d) M.
Hashimoto, K. Furukawa, T. Tomohiro and Y. Hatanaka, Chem. Pharm.
Bull., 2010, 58, 405; (e) J. A. Stewart, B. F. Piligian, S. R. Rundell and B.
M. Swarts, Chem. Commun., 2015, 51, DOI: 10.1039/c5cc07536j.
10 X. Zhao, G. Wu, Y. Zhang and J. Wang, Org. Lett., 2010, 12, 5580.
11 For reviews, see: (a) Q. Xiao, Y. Zhang and J. Wang, Acc. Chem. Res.,
2013, 46, 236; (b) Y. Xia, Y. Zhang and J. Wang, ACS Catal., 2013, 3,
2586; (c) Z. Liu and J. Wang, J. Org. Chem., 2013, 78, 10024; (d) F. Hu, Y.
Xia, C. Ma, Y. Zhang and J. Wang, Chem. Commun., 2015, 51, 7986.
12 For selected recent reports on the synthesis of 1,1-diaryl-substituted
olefins, see: (a) A. Hamze, A. Giraud, S. Messaoudi, O. Provot, J. F.
Peyrat, J. Bignon, J. M. Liu, J. Wdzieczak-Bakala, S. Thoret, J. Dubois, J.-
D. Brion and M. Alami, ChemMedChem 2009, 4, 1912; (b) A. Hamze, V.
Damien, O. Provot, J.-D. Brion and M. Alami, J. Org. Chem., 2009, 74,
1337; (c) X. Zhao, J. Jing, K. Lu, Y. Zhang and J. Wang, Chem. Commun.,
2010, 46, 1724; (d) A. Hamze, J.-D. Brion and M. Alami, Org. Lett., 2012,
14, 2782 and the references therein; (e) M. Roche, A. Hamze, O. Provot,
J.-D. Brion and M. Alami, J. Org. Chem., 2013, 78, 445; (f) M. Roche, S.
M. Salim, J. Bignon, H. Levaique, J.-D. Brion, M. Alami and A. Hazme, J.
Org. Chem., 2015, 80, 6715; (g) H, Tan, I. Houpis, R. Liu, Y. Wang and Z.
Chen, Org. Lett., 2015, 17, 3548.
Scheme 4 The proposed reaction mechanism
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2015, 00, 1-3 | 3
Please do not adjust margins