10.1002/anie.201814572
Angewandte Chemie International Edition
COMMUNICATION
Universities. We thank Prof. Donald A. Watson for his helpful
discussion.
Keywords: alkene difunctionalization • arylboration • nickel
catalysis • chain-walking • 1,1-diarylalkanes
[1]
Reviews on alkene difunctionalization: a) R. I. McDonald, G. Liu, S.
S.Stahl, Chem. Rev. 2011, 111, 2981-3019; b) V. Saini, B. J. Stokes, M.
S. Sigman, Angew. Chem. 2013, 125,11414-11429; Angew. Chem. Int.
Ed. 2013, 52, 11206-11220; c) G. Yin, X. Mu, G. Liu, Acc. Chem. Res.
2016, 49, 2413-2423; d) J. R. Coombs, J. P. Morken, Angew. Chem.
2016, 128, 2682-2696; Angew. Chem. Int. Ed. 2016, 55, 2636-2649; e)
J. Derosa, V. T. Tran, V. A. Van der Puyl, K. M. Engle, Chem. Sci. 2018,
9, 5278-5283.
[2]
[3]
For reviews: a) K. Semba, T. Fujihara, J. Terao, Y. Tsuji, Tetrahedron
2015, 71, 2183-2197; b) E. C. Neeve, S. J. Geier, I. A. I. Mkhalid, S. A.
Westcott, T. B. Marder, Chem. Rev. 2016, 116, 9091-9161; c) D.
Hemming, R. Fritzemeier, S. A. Westcott, W. L. Santos, P. G. Steel,
Chem. Soc. Rev. 2018, 47, 7477-7494.
1,2-arylboration by dual metal catalysis: a) K. Semba, Y. Nakao, J. Am.
Chem. Soc. 2014, 136, 7567-7570; b) K. B. Smith, K. M. Logan, W. You,
M. K. Brown, Chem. -Eur. J. 2014, 20, 12032-12036; c) K. M. Logan, K.
B. Smith, M. K. Brown, Angew. Chem. 2015, 127, 5317-5320; Angew.
Chem. Int. Ed. 2015, 54, 5228-5231; d) K. Semba, Y. Ohtagaki, Y.
Nakao, Org. Lett. 2016, 18, 3956-3959; e) K. M. Logan, M. K. Brown,
Angew. Chem. 2017, 129, 869-873; Angew. Chem. Int. Ed. 2017, 56,
851-855; f) K. B. Smith, M. K. Brown, J. Am. Chem. Soc. 2017, 139,
7721-7724; g) S. R. Sardini, M. K. Brown, J. Am. Chem. Soc. 2017, 139,
9823-9826. k) B. Chen, P. Cao, X. Yin, Y. Liao, L. Jiang, J. Ye, M.
Wang, J. Liao, ACS Catal. 2017, 7, 2425-2429.
Scheme 3. Mechanistic Studies
[4]
[5]
For a review: D. R. Pye, N. P. Mankad, Chem. Sci. 2017, 8, 1705-
1718.
Examples on alkene 1,2-arylborations with palladium catalysis: a) K.
Yang, Q. Song, J. Org. Chem. 2015, 81, 1000-1005; b) K. Yang, Q.
Song, Org. Lett. 2016, 18, 5460-5463.
[6]
[7]
A single example on alkene 1,2-arylborations with nickel catalysis: K. M.
Logan, S. R. Sardini, S. D. White, M. K. Brown, J. Am. Chem. Soc. 2018,
140, 159-162.
For reviews: a) A. Vasseur, J. Bruffaerts, I. Marek, Nat. Chem. 2016, 8,
209-219; b) H. Sommer, F. Juliá-Hernández, R. Martin, I. Marek, ACS
Cent. Sci. 2018, 4, 153-165; examples on 1,3-difunctionalization of
alkenes involving metal migration: c) R. T. Thornbury, V. Saini, T. A.
Fernandes, C. B. Santiago, E. P. A. Talbot, M. S. Sigman, J. M.
McKenna, F. D. Toste, Chem. Sci. 2017, 8, 2890-2897; d) W. Li, J. K.
Boon, Y. Zhao, Chem. Sci. 2018, 9, 600-607; e) P. Basnet, R. K.
Dhungana, S. Thapa, B. Shrestha, S. KC, J. M. Sears, R. Giri, J. Am.
Chem. Soc. 2018, 140, 7782-7786.
Scheme 4. Proposed Mechanism
Experimental Section
General Procedures: Under N2 atmosphere, to an oven-dried 10 mL
Schlenk tube, which was equipped with a magnetic stir bar and sealed
with a rubber stopper, sequentially there was added NiCl2·DME (11 mg,
0.05 mmol, 5 mol %), L5 (12.8 mg, 0.05 mmol, 5 mol %), LiOMe (57 mg,
1.5 mmol, 1.5 equiv) and bis(pinacolato)diboron (3a, 381 mg, 1.5 mmol,
1.5 equiv). Then anhydrous dioxane (5 mL), olefin (1, 1.2 mmol, 1.2
equiv) and arylhalide (2, 1.0 mmol, 1.0 equiv) were added. After 15 h of
stirring at 30 °C, an aliquot of 20 µL was removed and analyzed by GC.
The reaction mixture was diluted with 4 mL of ethyl acetate and the
resulting solution was filtered through Celite. The crude material was
concentrated in vacuo and separated on a silica gel column affording the
arylboration product.
[8]
[9]
Examples on alkene 1,1-arylboration reactions: a) H. M. Nelson, B. D.
Williams, J. Miró, F. D. Toste, J. Am. Chem. Soc. 2015, 137, 3213-3216.
b) A. M. Bergmann, S. K. Dorn, K. B. Smith, K. M. Logan, M. K. Brown,
Angew. Chem. 2019, 131, 1733-1737; Angew. Chem. Int. Ed. 2019, 58,
1719-1723.
Another strategy for 1,n-difunctionalization of alkenes is via 1,5-H shift,
for examples: a) P. Yu, J.-S. Lin, L. Li, S.-C. Zheng, Y.-P. Xiong, L.-J.
Zhao, B. Tan, X.-Y. Liu, Angew. Chem. 2014, 126, 12084-12088;
Angew. Chem. Int. Ed. 2014, 53, 11890-11894; b) P. Yu, S.-C. Zheng,
N.-Y. Yang, B. Tan, X.-Y Liu, Angew. Chem. 2015, 127, 4113-4117;
Angew. Chem. Int. Ed. 2015, 54, 4041-4045.
[10] a) S. Li, K. Huang, J. Zhang, W. Wu, X. Zhang, Org. Lett. 2013, 15,
1036-1039; b) Y. Yin, Y. Dai, H. Jia, J. Li, L. Bu, B. Qiao, X. Zhao, Z.
Jiang, J. Am. Chem. Soc. 2018, 140, 6083-6087.
Acknowledgements
[11] a) L. Peng, Y. Li, Y. Li, W. Wang, H. Pang, G. Yin, ACS Catal. 2018, 8,
310-313; b) L. Peng, Z. Li, Org. Lett. 2018, 20, 1880-1883.
We thank Profs. Q. Zhou, W.-B. Liu and A. Lei at Wuhan
University for the lent of lab space and share of the basic
instruments. We are grateful for the financial support from
National Natural Science Foundation of China (21702151,
21871211) and the Fundamental Research Funds for Central
[12] Leading examples on nickel chain-walking: a) J. S. Bair, Y. A. G.
Schramm, C. E. Sergeev, O. H. Eisenstein, J. F. J. Am. Chem. Soc.
2014, 136, 13098–13101; b) I. Buslov, J. Becouse, S. Mazza, M.
Montandon-Clerc, X. Hu, Angew. Chem. 2015, 127, 14731-14734;
Angew. Chem. Int. Ed. 2015, 54, 14523-14526; c) F. Juliá-Hernández,
T. Moragas, J. Cornella, R. Martin, Nature 2017, 545, 84-88; d) Y. He, Y.
This article is protected by copyright. All rights reserved.