Organic Letters
Letter
19601. (d) Cheng, X.-F.; Li, Y.; Su, Y.-M.; Yin, F.; Wang, J.-Y.; Sheng,
J.; Vora, H. U.; Wang, X.-S.; Yu, J.-Q. Pd(II)-Catalyzed
Enantioselective C-H Activation/C-O Bond Formation: Synthesis of
Chiral Benzofuranones. J. Am. Chem. Soc. 2013, 135, 1236−1239.
(e) Chu, L.; Wang, X.-C.; Moore, C. E.; Rheingold, A. L.; Yu, J.-Q.
Pd-catalyzed Enantioselective C-H Iodination: Asymmetric Synthesis
of Chiral Diarylmethylamines. J. Am. Chem. Soc. 2013, 135, 16344−
16347. (f) Chu, L.; Xiao, K.-J.; Yu, J.-Q. Room-temperature
enantioselective C-H iodination via kinetic resolution. Science 2014,
346, 451−455. (g) Chan, K. S. L.; Fu, H.-Y.; Yu, J.-Q. Palladium(II)-
Catalyzed Highly Enantioselective C-H Arylation of Cyclopropylme-
thylamines. J. Am. Chem. Soc. 2015, 137, 2042−2046. (h) Xiao, K.-J.;
Chu, L.; Yu, J.-Q. Enantioselective C-H Olefination of alpha-Hydroxy
and alpha-Amino Phenylacetic Acids by Kinetic Resolution. Angew.
Chem., Int. Ed. 2016, 55, 2856−2860. (i) Hu, L.; Shen, P.-X.; Shao,
Q.; Hong, K.; Qiao, J. X.; Yu, J.-Q. Pd(II)-Catalyzed Enantioselective
C(sp3)−H Activation/Cross-Coupling Reactions of Free Carboxylic
Acids. Angew. Chem., Int. Ed. 2019, 58, 2134−2138.
(5) (a) Yan, S.-B.; Zhang, S.; Duan, W.-L. Palladium-Catalyzed
Asymmetric Arylation of C(sp3)−H Bonds of Aliphatic Amides:
Controlling Enantioselectivity Using Chiral Phosphoric Amides/
Acids. Org. Lett. 2015, 17, 2458−2461. (b) Jain, P.; Verma, P.; Xia,
G.; Yu, J.-Q. Enantioselective Amine α-Functionalization via
Palladium-Catalysed C−H Arylation of Thioamides. Nat. Chem.
2017, 9, 140. (c) Wang, H.; Tong, H.-R.; He, G.; Chen, G. An
Enantioselective Bidentate Auxiliary Directed Palladium-Catalyzed
Benzylic C−H Arylation of Amines Using a BINOL Phosphate
Ligand. Angew. Chem., Int. Ed. 2016, 55, 15387−15391. (d) Yan, S.-
Y.; Han, Y.-Q.; Yao, Q.-J.; Nie, X.-L.; Liu, L.; Shi, B.-F. Palladium(II)-
Catalyzed Enantioselective Arylation of Unbiased Methylene C(sp3)−
H Bonds Enabled by a 2-Pyridinylisopropyl Auxiliary and Chiral
Phosphoric Acids. Angew. Chem., Int. Ed. 2018, 57, 9093−9097.
(6) Ye, B.; Cramer, N. Chiral Cyclopentadienyls: Enabling Ligands
for Asymmetric Rh(III)-Catalyzed C−H Functionalizations. Acc.
Chem. Res. 2015, 48, 1308−1318.
(7) (a) Sun, Y.; Cramer, N. Rhodium(III)-Catalyzed Enantiotopic
C−H Activation Enables Access to P-Chiral Cyclic Phosphinamides.
Angew. Chem., Int. Ed. 2017, 56, 364−367. (b) Sun, Y.; Cramer, N.
Rhodium(III)-Catalyzed Enantiotopic C−H Activation Enables
Access to P-Chiral Cyclic Phosphinamides. Chem. Sci. 2018, 9,
2981−2985.
(8) (a) Zheng, J.; You, S.-L. Construction of Axial Chirality by
Rhodium-Catalyzed Asymmetric Dehydrogenative Heck Coupling of
Biaryl Compounds with Alkenes. Angew. Chem., Int. Ed. 2014, 53,
13244−13247. (b) Zheng, J.; Cui, W.-J.; Zheng, C.; You, S.-L.
Synthesis and Application of Chiral Spiro Cp Ligands in Rhodium-
Catalyzed Asymmetric Oxidative Coupling of Biaryl Compounds with
Alkenes. J. Am. Chem. Soc. 2016, 138, 5242−5245. (c) Zheng, J.;
Wang, S.-B.; Zheng, C.; You, S.-L. Asymmetric Synthesis of
Spiropyrazolones by Rhodium-Catalyzed C(sp2)−H Functionaliza-
tion/Annulation Reactions. Angew. Chem., Int. Ed. 2017, 56, 4540−
4544.
ACKNOWLEDGMENTS
■
Financial support from the NSFC (21772170, 21572201) and
the Fundamental Research Funds for the Central Universities
(2018XZZX001-02) is gratefully acknowledged.
REFERENCES
(1) For selected recent reviews, see: (a) Gandeepan, P.; Mu
■
̈
ller, T.;
Zell, D.; Cera, G.; Warratz, S.; Ackermann, L. 3d Transition Metals
for C−H Activation. Chem. Rev. 2019, 119, 2192. (b) Piou, T.; Rovis,
T. Electronic and Steric Tuning of a Prototypical Piano Stool
Complex: Rh(III) Catalysis for C−H Functionalization. Acc. Chem.
Res. 2018, 51, 170. (c) Park, J.; Chang, S. Comparison of the
Reactivities and Selectivities of Group 9 [Cp*MIII] Catalysts in C−H
Functionalization Reactions. Chem. - Asian J. 2018, 13, 1089−1102.
(d) Yoshino, T.; Matsunaga, S. Cobalt-Catalyzed C(sp3)−H
Functionalization Reactions. Asian J. Org. Chem. 2018, 7, 1193−
1205. (e) Yoshino, T.; Matsunaga, S. (Pentamethylcyclopentadienyl)-
cobalt(III)-Catalyzed C−H Bond Functionalization: From Discovery
to Unique Reactivity and Selectivity. Adv. Synth. Catal. 2017, 359,
1245−1262. (f) Rej, S.; Chatani, N. Rh-Catalyzed Removable
Directing Group Assisted sp2 or sp3-C−H Bond Functionalization.
́
́
(g) Vasquez-Cespedes, S.; Wang, X.; Glorius, F. Plausible Rh(V)
Intermediates in Catalytic C−H Activation Reactions. ACS Catal.
2018, 8, 242−257. (h) Prakash, S.; Kuppusamy, R.; Cheng, C.-H.
Cobalt-Catalyzed Annulation Reactions via C−H Bond Activation.
ChemCatChem 2018, 10, 683−705. (i) Lied, F.; Patra, T.; Glorius, F.
Group 9 Transition Metal-Catalyzed C−H Halogenations. Isr. J.
Chem. 2017, 57, 945−952. (j) Moselage, M.; Li, J.; Ackermann, L.
Cobalt-Catalyzed C−H Activation. ACS Catal. 2016, 6, 498−525.
(k) Wei, D.; Zhu, X.; Niu, J.-L.; Song, M.-P. High-Valent-Cobalt-
Catalyzed C−H Functionalization Based on Concerted Metalation−
Deprotonation and Single-Electron-Transfer Mechanisms. Chem-
CatChem 2016, 8, 1242−1263. (l) Song, G.; Li, X. Substrate
Activation Strategies in Rhodium(III)-Catalyzed Selective Function-
alization of Arenes. Acc. Chem. Res. 2015, 48, 1007−1020.
(2) For selected reviews on asymmetric C−H functionalization, see:
(a) Saint-Denis, T. G.; Zhu, R.-Y.; Chen, G.; Wu, Q.-F.; Yu, J.-Q.
Enantioselective C(sp3)−H Bond Activation by Chiral Transition
Metal Catalysts. Science 2018, 359, 759. (b) Newton, C. G.; Wang, S.-
G.; Oliveira, C. C.; Cramer, N. Catalytic Enantioselective Trans-
formations Involving C−H Bond Cleavage by Transition-Metal
Complexes. Chem. Rev. 2017, 117, 8908. (c) Zheng, C.; You, S.-L.
Recent Development of Direct Asymmetric Functionalization of Inert
C−H Bonds. RSC Adv. 2014, 4, 6173. (d) Wencel-Delord, J.;
Colobert, F. Asymmetric C(sp2)−H Activation. Chem. - Eur. J. 2013,
19, 14010−14017. (e) Giri, R.; Shi, B.-F.; Engle, K. M.; Maugel, N.;
Yu, J.-Q. Transition Metal-Catalyzed C-H Activation Reactions:
Diastereoselectivity and Enantioselectivity. Chem. Soc. Rev. 2009, 38,
3242−3272.
(3) Selected reviews: (a) Lapointe, D.; Fagnou, K. Overview of the
Mechanistic Work on the Concerted Metallation−Deprotonation
Pathway. Chem. Lett. 2010, 39, 1118−1126. (b) Ackermann, L.
Carboxylate-Assisted Transition-Metal-Catalyzed C−H Bond Func-
tionalizations: Mechanism and Scope. Chem. Rev. 2011, 111, 1315−
1345. (c) Engle, K. M. The Mechanism of Palladium(II)-Mediated
C−H Cleavage with mono-N-Protected Amino Acid (MPAA)
ligands: Origins of Rate Acceleration. Pure Appl. Chem. 2016, 88,
119−138.
(9) (a) Shen, B.; Wan, B.; Li, X. Enantiodivergent Desymmetrization
in the Rhodium(III)-Catalyzed Annulation of Sulfoximines with
Diazo Compounds. Angew. Chem., Int. Ed. 2018, 57, 15534−15538.
(10) For the cooperative effect of chiral Cpx ligands and chiral
carboxylic acids, see: (a) Jang, Y.-S.; Dieckmann, M.; Cramer, N.
Cooperative Effects between Chiral Cpx−Iridium(III) Catalysts and
Chiral Carboxylic Acids in Enantioselective C−H Amidations of
Phosphine Oxides. Angew. Chem., Int. Ed. 2017, 56, 15088−15092.
(b) Sun, Y.; Cramer, N. Enantioselective Synthesis of Chiral-at-Sulfur
1,2-Benzothiazines by CpxRhIII-Catalyzed C−H Functionalization of
Sulfoximines. Angew. Chem., Int. Ed. 2018, 57, 15539−15543.
(4) For selected examples, see: (a) Shi, B.-F.; Maugel, N.; Zhang, Y.-
H.; Yu, J.-Q. PdII-Catalyzed Enantioselective Activation of C(sp2)−H
and C(sp3)−H Bonds Using Monoprotected Amino Acids as Chiral
Ligands. Angew. Chem., Int. Ed. 2008, 47, 4882−4886. (b) Shi, B.-F.;
Zhang, Y.-H.; Lam, J. K.; Wang, D.-H.; Yu, J.-Q. Pd(II)-Catalyzed
Enantioselective C−H Olefination of Diphenylacetic Acids. J. Am.
Chem. Soc. 2010, 132, 460−461. (c) Wasa, M.; Engle, K. M.; Lin, D.
W.; Yoo, E. J.; Yu, J.-Q. Pd(II)-Catalyzed Enantioselective C-H
Activation of Cyclopropanes. J. Am. Chem. Soc. 2011, 133, 19598−
́
(c) Jang, Y.-S.; Wozniak; Pedroni, J.; Cramer, N. Access to P- and
Axially Chiral Biaryl Phosphine Oxides by Enantioselective CpxIrIII-
Catalyzed C−H Arylations. Angew. Chem., Int. Ed. 2018, 57, 12901−
12905.
(11) For selected examples of enantioselective C−H functionaliza-
tions via chiral CpxM(III)-catalyzed stereodetermining migratory
D
Org. Lett. XXXX, XXX, XXX−XXX