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ACS Catalysis
Huang, Z.; Lim, H. N.; Mo, F.; Young, M. C.; Dong, G. Transition
metal-catalyzed ketone-directed or mediated C–H
Direct Arylation of C–H Bonds with Diaryliodonium Salts. J. Am.
Chem. Soc. 2015, 137, 12231-12240. (c) Yang, W.; Ye, S.; Fanning, D.;
Coon, T.; Schmidt, Y.; Krenitsky, P.; Stamos, D.; Yu, J.-Q.
Orchestrated Triple C–H Activation Reactions Using Two
Directing Groups: Rapid Assembly of Complex Pyrazoles. Angew.
Chem. Int. Ed. 2015, 54, 2501-2504. (d) Yu, S.; Tang, G.; Li, Y.; Zhou,
X.; Lan, Y.; Li, X. Anthranil: An Aminating Reagent Leading to
Bifunctionality for Both C(sp3)−H and C(sp2)−H under
Rhodium(III) Catalysis. Angew. Chem. Int. Ed. 2016, 55, 8696-8700.
(e) Xu, J.-W.; Zhang, Z.-Z.; Rao, W.-H.; Shi, B.-F. Site-Selective
Alkenylation of δ-C(sp3)–H Bonds with Alkynes via a Six-
Membered Palladacycle. J. Am. Chem. Soc. 2016, 138, 10750-10753.
(f) Yada, A.; Liao, W.; Sato, Y.; Murakami, M. Buttressing
Salicylaldehydes: A Multipurpose Directing Group for C(sp3)−H
Bond Activation. Angew. Chem. Int. Ed. 2017, 56, 1073-1076. (g) Liu,
Y.; Ge, H. Site-selective C–H arylation of primary aliphatic amines
enabled by a catalytic transient directing group. Nat. Chem. 2017,
9, 26-32. (h) Gulia, N.; Daugulis, O. Palladium-Catalyzed
Pyrazole-Directed sp3 C−H Bond Arylation for the Synthesis of β-
Phenethylamines. Angew. Chem. Int. Ed. 2017, 56, 3630-3634. (i)
Chen, G.; Zhuang, Z.; Li, G.-C.; Saint-Denis, T. G.; Hsiao, Y.; Joe,
C. L.; Yu, J.-Q. Ligand-Enabled β-C–H Arylation of α-Amino Acids
Without Installing Exogenous Directing Groups. Angew. Chem.
Int. Ed. 2017, 56, 1506-1509.
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functionalization. Chem. Soc. Rev. 2015, 44, 7764-7786. (f) He, G.;
Wang, B.; Nack, W. A.; Chen, G. Syntheses and Transformations
of α-Amino Acids via Palladium-Catalyzed Auxiliary-Directed sp3
C–H Functionalization. Acc. Chem. Res. 2016, 49, 635-645. (g) He,
J.; Wasa, M.; Chan, K. S. L.; Shao, Q.; Yu, J.-Q. Palladium-
Catalyzed Transformations of Alkyl C–H Bonds. Chem. Rev. 2017,
117, 8754-8786. (h) Ping, L.; Chung, D. S.; Bouffard, J.; Lee, S.-g.
Transition metal-catalyzed site- and regio-divergent C–H bond
functionalization. Chem. Soc. Rev. 2017, 46, 4299-4328. (i) Park,
Y.; Kim, Y.; Chang, S. Transition Metal-Catalyzed C–H Amination:
Scope, Mechanism, and Applications. Chem. Rev. 2017, 117, 9247-
9301. (j) Gensch, T.; James, M.; Dalton, T.; Glorius, F. Increasing
Catalyst Efficiency in C−H Activation Catalysis. Angew. Chem. Int.
Ed. 2018, 57, 2296-2306. (k) Sambiagio, C.; Schönbauer, D.; Blieck,
R.; Dao-Huy, T.; Pototschnig, G.; Schaaf, P.; Wiesinger, T.; Farooq
Zia, M.; Wencel-Delord, J.; Besset, T.; Maesa, B. U. W.; Schnürch,
M. A comprehensive overview of directing groups applied in
metal-catalysed C–H functionalisation chemistry. Chem. Soc. Rev.
2018, 47, 6603-6743. (l) Rej, S.; Chatani, N. Rh-Catalyzed
Removable Directing Group Assisted sp2 or sp3-C‒H Bond
Functionalization. Angew. Chem. Int. Ed. 2018, 57,
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(6) Some examples on non-directed C(sp3)–H bond
functionalization of silyl methyl group have been reported.
Borylation: (a) Ohmura, T.; Torigoe, T.; Suginome, M. Catalytic
Functionalization of Methyl Group on Silicon: Iridium-Catalyzed
C(sp3)–H Borylation of Methylchlorosilanes. J. Am. Chem. Soc.
2012, 134, 17416-17419. (b) Ohmura, T.; Torigoe, T.; Suginome, M.
(8) Review and recent examples on silicon tethers bearing a DG
for C(sp2)−H functionalization, see: (a) Wang, C.; Ge, H. Silanol as
a Removable Directing Group for the PdII-Catalyzed Direct
Olefination of Arenes. Chem. Eur. J. 2011, 17, 14371-14374. (b)
Gulevich, A. V.; Melkonyan, F. S.; Sarkar, D.; Gevorgyan, V.
Double-Fold C–H Oxygenation of Arenes Using PyrDipSi: a
General and Efficient Traceless/Modifiable Silicon-Tethered
Directing Group. J. Am. Chem. Soc. 2012, 134, 5528-5531. (c) Sarkar,
D.; Melkonyan, F. S.; Gulevich, A. V.; Gevorgyan, V. Twofold
Unsymmetrical C-H Functionalization of PyrDipSi-Substituted
Arenes: A General Method for the Synthesis of Substituted
meta-Halophenols. Angew. Chem. Int. Ed. 2013, 52, 10800-10804.
(d) Lee, S.; Lee, H.; Tan, K. L. Meta-Selective C–H
Functionalization Using a Nitrile-Based Directing Group and
Cleavable Si-Tether. J. Am. Chem. Soc. 2013, 135, 18778-18781. (e)
Sarkar, D.; Gulevich, A. V.; Melkonyan, F. S.; Gevorgyan, V.
Synthesis of Multisubstituted Arenes via PyrDipSi-Directed
Unsymmetrical Iterative C–H Functionalizations. ACS Catal. 2015,
5, 6792-6801. (f) Wang, Y.; Gevorgyan, V. General Method for the
Synthesis of Salicylic Acids from Phenols through
Palladium-Catalyzed Silanol-Directed C-H Carboxylation. Angew.
Chem. Int. Ed. 2015, 54, 2255-2259. (g) Parasram, M.; Gevorgyan,
V. Silicon-Tethered Strategies for C–H Functionalization
Reactions. Acc. Chem. Res. 2017, 50, 2038-2053. (h) Wang, Y.;
Gevorgyan, V. Synthesis of Active Hexafluoroisopropyl Benzoates
through a Hydrogen-Bond-Enabled Palladium(II)-Catalyzed C−H
Alkoxycarbonylation Reaction. Angew. Chem. Int. Ed. 2017, 56,
3191-3195.
Functionalization
of
Tetraorganosilanes
and
Permethyloligosilanes at a Methyl Group on Silicon via Iridium-
Catalyzed C(sp3)–H Borylation. Organometallics, 2013, 32, 6170-
6173. (c) Huang, G.; Kalek, M.; Liao, R.-Z.; Himo, F. Mechanism,
reactivity, and selectivity of the iridium-catalyzed C(sp3)–H
borylation of chlorosilanes. Chem. Sci. 2015, 6, 1735-1746. (d)
Ohmura, T.; Sasaki, I.; Torigoe, T.; Suginome, M.
A
(Borylmethyl)silane Bearing Three Hydrolyzable Groups on
Silicon: Synthesis via Iridium-Catalyzed C(sp3)–H Borylation and
Conversion to Functionalized Siloxanes. Organometallics, 2016,
35, 1601-1603. (e) Torigoe, T.; Ohmura, T.; Suginome, M.
Utilization of a Trimethylsilyl Group as a Synthetic Equivalent of
a Hydroxyl Group via Chemoselective C(sp3)–H Borylation at the
Methyl Group on Silicon. J. Org. Chem. 2017, 82, 2943-2956. (f)
Murai, M.; Takeuchi, Y.; Takai, K. Iridium-catalyzed
Dehydrogenative Dimerization of Benzylmethylsilanes via
Silylation of C(sp3)–H Bonds Adjacent to a Silicon Atom. Chem.
Lett. 2017, 46, 1044-1047. Intramolecular coupling: (g) Liang, Y.;
Geng, W.; Wei, J.; Ouyang, K.; Xi, Z. Palladium-catalyzed silyl
C(sp3)–H bond activation. Org. Biomol. Chem. 2012, 10, 1537-1542.
(h) Mistico, L.; Querolle, O.; Meerpoel, L.; Angibaud, P.;
Durandetti, M.; Maddaluno, J. Access to Silylated Pyrazole
Derivatives by Palladium-Catalyzed C−H Activation of a TMS
group. Chem. Eur. J. 2016, 22, 9687-9692. Radical cyclization: (i)
Yang, Y.; Song, R.-J.; Li, Y.; Ouyang, X.-H.; Li, J.-H.; He, D.-L.
Oxidative radical divergent Si-incorporation: facile access to Si-
containing heterocycles. Chem. Commun. 2018, 54, 1441-1444. (j)
Wu, L.-J.; Yang, Y.; Song, R.-J.; Yu, J.-X.; Li, J.-H.; He, D.-L. An
access to 1,3-azasiline-fused quinolinones via oxidative
heteroannulation involving silyl C(sp3)–H functionalization.
Chem. Commun. 2018, 54, 1367-1370.
(9) The C(sp3)−H olefination of silylmethyl group in the presence
of a stoichiometric amount of palladium(II) catalyst and two
equivalents of copper(II) acetate was reported, see: (a) Wang, C.;
Ge,
H.
Palladium-Mediated
Olefination
of
2-(tert-
Butyldimethylsilyl)pyridine by sp3 C–H Activation. Synthesis 2011,
16, 2590–2594. A single example with 36% yield on C(sp3)−H
alkylation of silyl methyl group was presented, see: (b) Zhang, Y.;
Jiang, H.; Chen, D.; Zhang, Y. Amino acid-promoted C–H
alkylation with alkylboronic acids using a removable directing
group. Org. Biomol. Chem. 2016, 14, 4585-4589.
(7) Some recent examples on transition metal-catalyzed directed
C−H functionalization of C-bound methyl group: (a) He, C.;
Gaunt, M. J. Ligand-Enabled Catalytic C−H Arylation of Aliphatic
Amines by a Four-Membered-Ring Cyclopalladation Pathway.
Angew. Chem. Int. Ed. 2015, 54, 15840-15844. (b) Gao, P.; Guo, W.;
Xue, J.; Zhao, Y.; Yuan, Y.; Xia, Y.; Shi, Z. Iridium(III)-Catalyzed
(10) (a) Itami, K.; Kamei, T.; Yoshida, J.-i. Unusually Accelerated
Silylmethyl Transfer from Tin in Stille Coupling: Implication of
Coordination-Driven Transmetalation. J. Am. Chem. Soc. 2001,
123, 8773-8779; (b) Itami, K.; Mineno, M.; Kamei, T.; Yoshida, J.-i.
A General and Straightforward Route toward Diarylmethanes.
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