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COMMUNICATION
Journal Name
Knowles, J. Am. Chem. Soc., 2016, 138, 1D0O7I:9140-.11003799/7D;0(CbC) 0E2. 3O0t6aJ,
H. Wang, N. L. Frye and R. R. Knowles, J. Am. Chem. Soc., 2019,
dehydroxyalkylative halogenation reaction is primarily limited
to ortho electron-withdrawing substituted aryl alcohols at this
stage, and aldehyde products were mainly generated from non-
ortho-substituted substrates (Figure S4). This ortho-substituent
1
41, 1457-1462; (c) M. Wang, J. Lu, L. Li, H. Li, H. Liu and F. Wang,
J. Catal., 2017, 348, 160-167; (d) A. Xia, X. Qi, X. Mao, X. Wu, X.
Yang, R. Zhang, Z. Xiang, Z. Lian, Y. Chen and S. Yang, Org. Lett.,
effect has also been observed in other decarboxylative
2
019, 21, 3028-3033.
. (a) S. T. Nguyen, P. R. D. Murray and R. R. Knowles, ACS Catal.,
020, 10, 800-805; (b) M. Liu, Z. Zhang, X. Shen, H. Liu, P. Zhang,
B. Chen and B. Han, Chem. Commun., 2019, 55, 925-928.
reactions reported previously.1
0a, 13
On one hand, ortho-
4
substituted substrates are inherently less stable in compariosn
to their meta- and para-substituted substrates. On the other
2
hand, the presence of an ortho-electron-withdrawing 5. M. Liu, Z. Zhang, J. Song, S. Liu, H. Liu and B. Han, Angew. Chem.
substituent group could potentially stablize the transition state.
Int. Ed., 2019, 58, 17393-17398.
These two electronic effects could cooperatively reduce the 6. (a) K. Zhang, L. Chang, Q. An, X. Wang and Z. Zuo, J. Am. Chem.
Soc., 2019, 141, 10556-10564; (b) X. Wu, F. A. Cruz, A. Lu and V.
M. Dong, J. Am. Chem. Soc., 2018, 140, 10126-10130.
. (a) H. Wang, I. Choi, T. Rogge, N. Kaplaneris and L. Ackermann,
Nat. Catal., 2018, 1, 993-1001; (b) P. Zhao, C. D. Incarvito and J.
F. Hartwig, J. Am. Chem. Soc., 2006, 128, 3124-3125; (c) Y. Terao,
H. Wakui, T. Satoh, M. Miura and M. Nomura, J. Am. Chem. Soc.,
activation barriers and promote decarbonylative halogenation
reaction. In addition, the possible transformation pathway of
primary alcohol substrates (1p) is given in Fig. S5.4b, 5
1
4
7
8
9
In summary, we discovered that aryl halides could be
synthesized by dehydroxyalkylative halogenation of C(aryl)−C
bond of aryl alcohols, using oxygen as the oxidant and Cu
halides as both catalyst and halide source. Aryl alcohols served
as aromatic electrophilic or radical synthetic equivalents in the
reaction, and were efficiently converted into aryl halides
2001, 123, 10407-10408.
. (a) H. Li, Y. Li, X.-S. Zhang, K. Chen, X. Wang and Z.-J. Shi, J. Am.
Chem. Soc., 2011, 133, 15244-15247; (b) E. Ozkal, B. Cacherat and
B. Morandi, ACS Catal., 2015, 5, 6458-6462; (c) Y. Qiu, A.
Scheremetjew and L. Ackermann, J. Am. Chem. Soc., 2019, 141,
(
chlorides, bromides and iodides) in excellent yields. The
2731-2738.
reaction proceeds via dehydrogenation of alcohol substrate,
C(CO)−C bonds cleavage of ketone, and decarbonylaꢀve
halogenation of aldehyde intermediate. Since C(aryl)-C(OH)
bonds represent the most predominent motifs in the linkages
of lignin, we believe that this new method to synthesize aryl
halides will inspire explorations for the activation and
functionalization of C(aryl)−C bonds and has promising
potential for valorization of lignin to produce high-value
products, and further research is currently ongoing.
. (a) C. Le, T. Q. Chen, T. Liang, P. Zhang and D. W. C. MacMillan,
Science, 2018, 360, 1010; (b) J. Latham, E. Brandenburger, S. A.
Shepherd, B. R. K. Menon and J. Micklefield, Chem. Rev., 2018,
118, 232-269; (c) S. Mori, A. H. Pang, N. Thamban Chandrika, S.
Garneau-Tsodikova and O. V. Tsodikov, Nat. Commun., 2019, 10,
1255; (d) J. Wang, M. Sánchez-Roselló, J. L. Aceña, C. del Pozo, A.
E. Sorochinsky, S. Fustero, V. A. Soloshonok and H. Liu, Chem.
Rev., 2014, 114, 2432-2506.
1
0. (a) N. Rodríguez and L. J. Goossen, Chem. Soc. Rev., 2011, 40,
5030-5048; (b) Z. Wang, L. Zhu, F. Yin, Z. Su, Z. Li and C. Li, J. Am.
Chem. Soc., 2012, 134, 4258-4263; (c) T. Nishikata, S. Ishida and
R. Fujimoto, Angew. Chem. Int. Ed., 2016, 55, 10008-10012; (d)
D. A. Petrone, J. Ye and M. Lautens, Chem. Rev., 2016, 116, 8003-
8104; (e) G. J. P. Perry, J. M. Quibell, A. Panigrahi and I. Larrosa,
J. Am. Chem. Soc., 2017, 139, 11527-11536; (f) F. Mo, D. Qiu, Y.
Zhang and J. Wang, Acc. Chem. Res., 2018, 51, 496-506.
Conflicts of interest
There are no conflicts to declare.
1
1. (a) J. Piera and J.-E. Bäckvall, Angew. Chem. Int. Ed., 2008, 47,
Acknowledgements
The authors thank the National Natural Science Foundation of
China (21972146, 21733011), Beijing Municipal Science &
Technology Commission (Z181100004218004), National Key
3
2
506-3523; (b) B. L. Ryland and S. S. Stahl, Angew. Chem. Int. Ed.,
014, 53, 8824-8838.
1
2. (a) S. Tang, Y. Liu, X. Gao, P. Wang, P. Huang and A. Lei, J. Am.
Chem. Soc., 2018, 140, 6006-6013; (b) S. Paul and J. Guin, Chem.
Eur. J., 2015, 21, 17618-17622; (c) Z. Zong, W. Wang, X. Bai, H. Xi
and Z. Li, Asian J. Org. Chem, 2015, 4, 622-625; (d) W.-C. Yang, J.-
G. Feng, L. Wu and Y.-Q. Zhang, Adv. Synth. Catal., 2019, 361,
Research
(
(
and
2017YFA0403103), and the Chinese Academy of Sciences
QYZDY-SSW-SLH013).
Development
Program
of
China
1700-1709.
1
3. (a) M. Pichette Drapeau, J. Bahri, D. Lichte and L. J. Gooßen,
Angew. Chem. Int. Ed., 2019, 58, 892-896; (b) J. Schwarz and B.
König, Green Chem., 2018, 20, 323-361; (c) T. Patra and D. Maiti,
Chem. Eur. J., 2017, 23, 7382-7401; (d) L. J. Gooßen, N. Rodríguez
and K. Gooßen, Angew. Chem. Int. Ed., 2008, 47, 3100-3120.
4. (a) L. Xue, W. Su and Z. Lin, Dalton Trans., 2011, 40, 11926-11936;
Notes and references
1. (a) C. Li, X. Zhao, A. Wang, G. W. Huber and T. Zhang, Chem. Rev.,
2
015, 115, 11559-11624; (b) R. Rinaldi, R. Jastrzebski, M. T.
Clough, J. Ralph, M. Kennema, P. C. A. Bruijnincx and B. M.
Weckhuysen, Angew. Chem. Int. Ed., 2016, 55, 8164-8215; (c) Z.
Zhang, J. Song and B. Han, Chem. Rev., 2017, 117, 6834-6880; (d)
Z. Sun, B. Fridrich, A. de Santi, S. Elangovan and K. Barta, Chem.
Rev., 2018, 118, 614-678.
1
(
b) F. Garcia-Martin, T. Matsushita, H. Hinou and S.-I. Nishimura,
Chem. Eur. J., 2014, 20, 15891-15902.
2. M. Wang, J. Ma, H. Liu, N. Luo, Z. Zhao and F. Wang, ACS Catal.,
2018, 8, 2129-2165.
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| J. Name., 2012, 00, 1-3
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