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complementary catalysts for the C‒H activation and transformation
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1597–1600. (g) Sharma, R.; Kumar, I.; Kumar, R.; Sharma, U.
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Activated and Unactivated Olefins: Mechanistic Study and Total
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(h) Zhang, Z.; Tanaka, K.; Yu, J.-Q. Remote site-selective C-H
activation directed by a catalytic bifunctional template. Nature 2017,
Catalyzed Sequential Silylation and Borylation of Heteroarenes Based
on Regioselective C-H Bond Activation. Angew. Chem. Int. Ed. 2018,
Functionalization of Remote C–H Bonds in Adjacent Positions. Nat.
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(4) Selected reviews on C-H alkylation: (a) Dong, Z.; Ren, Z.;
Thompson, S. J.; Xu, Y.; Dong, G. Transition-Metal-Catalyzed C-H
Alkylation Using Alkenes. Chem. Rev. 2017, 117, 9333–9403. (b)
Evano, G.; Theunissen, C. Beyond Friedel and Crafts: Directed
Alkylation of C-H Bonds in Arenes. Angew. Chem. Int. Ed. 2019, 58,
(5) Selected reviews on regiodivergent C-H functionalization: (a)
Mahatthananchai, J.; Dumas, A. M.; Bode, J. W. Catalytic Selective
Synthesis. Angew. Chem. Int. Ed. 2012, 51, 10954-10990. (b) Ping. L.;
Chung, D. S.; Bouffard, J.; Lee, S. Transition Metal-catalyzed Site- and
Regio-divergent C–H bond Functionalization. Chem. Soc. Rev. 2017,
catalyzed Regiodivergent Organic Reactions. Chem. Soc. Rev. 2019, 48,
4515-4618.
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of quinolines and related organic compounds.
ASSOCIATED CONTENT
The Supporting Information is available free of charge on the ACS
Publications website.
Detailed experimental procedures, computational details,
spectroscopic data for all new compounds (PDF)
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Crystallographic data for 3ag (CCDC 1979509) and 4ag (CCDC
1979510) (CIF)
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AUTHOR INFORMATION
Corresponding Author
*luogen@ahu.edu.cn
*houz@riken.jp
ORCID
Shao-Jie Lou: 0000-0003-3700-6812
Liang Zhang: 0000-0002-5661-3557
Masayoshi Nishiura: 0000-0003-2748-9814
Gen Luo: 0000-0002-5297-6756
Yi Luo: 0000-0001-6390-8639
Zhaomin Hou: 0000-0003-2841-5120
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
(6) Recent reviews: (a) Nishiura, M.; Guo, F.; Hou, Z. Half-Sandwich
Rare-Earth-Catalyzed Olefin Polymerization, Carbometalation, and
Hydroarylation. Acc. Chem. Res. 2015, 48, 2209−2220. (b) P. L.;
Arnold, MacMullon, M. W.; Rieb, J.; Kühn, F. E. C-H bond Activation
by f-block Complexes. Angew. Chem. Int. Ed. 2015, 54, 82−100. (c)
Rev. 2018, 376, 506-532. (d) Gandeepan, P.; Müller, T.; Zell, D.; Cera,
G.; Warratz, S.; Ackermann, L. 3d Transition Metals for C–H
Activation. Chem. Rev. 2019, 119, 2192-2452
This work was supported in part by JSPS KAKENHI Grants
(JP19H00897, JP17H06451). We gratefully appreciate accesses to
RICC (RIKEN Integrated Cluster of Clusters), the Network and
Information Centre of Dalian University of Technology, and the
High-performance Computing Platform of Anhui University for
computational resources. G.L. thanks the Innovation and
Entrepreneurship Project of Overseas Returnees in Anhui Province
(No. 2020LCX006). We also thank Mrs. Akiko Karube for high
resolution mass spectrometry (HRMS) analyses.
(7) Selected examples: (a) Guan, B.-T.; Hou, Z. Rare-Earth-Catalyzed
C–H Bond Addition of Pyridines to Olefins. J. Am. Chem. Soc. 2011,
133, 18086−18089. (b) Oyamada, J.; Hou, Z. Regioselective C-H
Alkylation of Anisoles with Olefins Catalyzed by Cationic Half-
Sandwich Rare Earth Alkyl Complexes. Angew. Chem. Int. Ed. 2012,
51, 12828-12832. (c) Guan, B.-T.; Wang, B.; Nishiura, M.; Hou, Z.
Yttrium-Catalyzed Addition of Benzylic C-H Bonds of Alkyl Pyridines
to Olefins. Angew. Chem. Int. Ed. 2013, 52, 4418-4421. (d) Song, G.;
W. N. O, W.; Hou, Z. Enantioselective C-H Bond Addition of Pyridines
to Alkenes Catalyzed by Chiral Half-Sandwich Rare-Earth Complexes.
J. Am. Chem. Soc. 2014, 136, 12209−12212. (e) Song, G.; Wang, B.;
Nishiura, M.; Hou, Z. Catalytic C-H Bond Addition of Pyridines to
Allenes by a Rare-Earth Catalyst. Chem. Eur. J. 2015, 21, 8394−8398.
(f) Song, G.; Luo, G.; Oyamada, J.; Luo, Y.; Hou, Z. ortho-Selective
C-H Addition of N,N-dimethyl Anilines to Alkenes by a Yttrium
Catalyst. Chem. Sci. 2016, 7, 5265-5270. (g) Shi, X.; Nishiura, M.; Hou.
Z. C-H Polyaddition of Dimethoxyarenes to Unconjugated Dienes by
Rare Earth Catalysts. J. Am. Chem. Soc. 2016, 138, 6147−6150. (h) Shi,
X.; Nishiura, M.; Hou. Z. Simultaneous Chain-Growth and Step-
Growth Polymerization of Methoxystyrenes by Rare-Earth Catalysts.
Angew. Chem. Int. Ed. 2016, 55, 14812-14817. (i) Luo, Y.; Teng, H.-
L.; Nishiura, M.; Hou. Z. Asymmetric Yttrium-Catalyzed C(sp3)-H
Addition of 2-Methyl Azaarenes to Cyclopropenes. Angew. Chem. Int.
Ed. 2017, 56, 9207-9210. (j) Luo, Y.; Ma, Y.; Hou. Z. α-C-H
Alkylation of Methyl Sulfides with Alkenes by a Scandium Catalyst. J.
Am. Chem. Soc. 2018, 140, 114−117. (k) Xue, C.; Luo, Y.; Teng, H.;
Ma, Y.; Nishiura, M.; Hou, Z. Ortho-Selective C−H Borylation of
Aromatic Ethers with Pinacolborane by Organo Rare-Earth Catalysts.
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