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ACS Catalysis
1
2
3
4
5
6
7
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Chiral Ferrocenes by Transition-Metal-Catalyzed Enantioselective
2014, 53, 2443-2446. (d) Wang, C.; Zhang, L.; Chen, C.-P; Han, J.;
Yao, Y.-M.; Zhao, Y.-S. Oxalyl amide assisted palladium-catalyzed
synthesis of pyrrolidones via carbonylation of γ-C(sp3)-H bonds of
aliphatic amine substrates. Chem. Sci. 2015, 6, 4610-4614. (e) Lopez,
B.; Rodriguez, A.; Santos, D.; Albert, J.; Ariza, X.; Garcia, J.; Granell,
J. Preparation of benzolactams by Pd(II)-catalyzed carbonylation of
N-unprotected arylethylamines. Chem. Commun. 2011, 47, 1054-1056.
(f) Giri, R.; Lam, J. K.; Yu, J.-Q., Synthetic Applications of Pd(II)-
Catalyzed C−H Carboxylation and Mechanistic Insights: Expedient
Routes to Anthranilic Acids, Oxazolinones, and Quinazolinones. J.
Am. Chem. Soc. 2010, 132, 686–693.
(9) (a) Willcox, D.; Chappell, B. G. N.; Hogg, K. F.; Calleja, J.;
Smalley, A. P.; Gaunt, M. J. A general catalytic β-C−H carbonylation
of aliphatic amines to β-lactams. Science 2016, 354, 851-857. (b)
McNally, A.; Haffemayer, B.; Collins, B. S. L.; Gaunt, M. J. Palladi-
um-catalysed C−H activation of aliphatic amines to give strained
nitrogen heterocycles. Nature 2014, 510, 129-133. (c) Hogg, K. F.;
Trowbridge, A.; Alvarez-Perez, A.; Gaunt, M. J. The α-tertiary amine
motif drives remarkable selectivity for Pd-catalyzed carbonylation of
β-methylene C−H bonds. Chem. Sci. 2017, 8, 8198-8203. (d) Cabrera-
Pardo, J. R.; Trowbridge, A.; Nappi, M.; Ozaki, K.; Gaunt, M. J.
Selective Palladium(II)-Catalyzed Carbonylation of Methylene -
C−H Bonds in Aliphatic Amines. Angew. Chem. Int. Ed. 2017, 56,
11958-11962.
(10) For selected examples see: (a) 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. (b) Chan, K. S.; Fu, H.-Y.;
Yu, J.-Q. Palladium(II)-Catalyzed Highly Enantioselective C−H Ary-
lation of Cyclopropylmethylamines. J. Am. Chem. Soc. 2015, 137,
2042-2046. (c) Laforteza, B. N.; Chan, K. S. L.; Yu, J.-Q. Enantiose-
lective ortho-C−H Cross-Coupling of Diarylmethylamines with Or-
ganoborons. Angew. Chem. Int. Ed. 2015, 54, 11143-11146. (d) Xiao,
K.-J.; Chu, L.; Yu, J.-Q. Enantioselective C−H Olefination of -
Hydroxy and -Amino Phenylacetic Acids by Kinetic Resolution.
Angew. Chem. Int. Ed. 2016, 55, 2856-2860. Chu, Ling; Xiao, K.-J.;
Yu, J.-Q. Room-temperature enantioselective C–H iodinationvia ki-
netic resolution. 2014, 346, 451-455.
(11) (a) Lu, Y.; Leow, D.; Wang, X.-S.; Engle, K. M.; Yu, J.-Q.
Hydroxyl-directed C–H carbonylation enabled by mono-N-protected
amino acid ligands: An expedient route to 1-isochromanones. Chem.
Sci. 2011, 2, 967-971. (b) 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.
C−H Activation. ChemCatChem 2016, 8, 68-73. (b) Cui, Y.-M.; Lin,
Y.; Xu, L.-W. Catalytic synthesis of chiral organoheteroatom com-
pounds of silicon, phosphorus, and sulfur via asymmetric transition
metal-catalyzed C–H functionalization. Coord. Chem. Rev. 2017, 330,
37-52. (c) 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, DOI: 10.1126/science.aao4798. (d)
Newton, C. G.; Wang, S.-G.; Oliveira, C. C.; Cramer, N. Catalytic
Enantioselective Transformations Involving C−H Bond Cleavage by
Transition-Metal Complexes. Chem. Rev. 2017, 117, 8908-8976.
(4) For selected reviews on C−H carbonylation see: (a) Liu, Q.;
Zhang, H.; Lei, A.-W. Oxidative Carbonylation Reactions:
Organometallic Compounds (R-M) or Hydrocarbons (R-H) as
Nucleophiles. Angew. Chem. Int. Ed. 2011, 50, 10788-10799. (b) Wu,
X.-F.; Neumann, H.; Beller, M. Palladium-Catalyzed Oxidative
Carbonylation Reactions. ChemSusChem 2013, 6, 229-241. (c) Liu,
B.; Hu, F.; Shi, B.-F. Recent Advances on Ester Synthesis via Transi-
tion-Metal Catalyzed C−H Functionalization. ACS Catalysis 2015, 5,
1863-1881.
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10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(5) Dailler, D.; Rocaboy, R.; Baudoin, O. Synthesis of -Lactams
by Palladium(0)-Catalyzed C(sp3)−H Carbamoylation. Angew. Chem.
Int. Ed. 2017, 56, 7218-7222.
(6) (a) Speck, K.; Magauer, T. The chemistry of isoindole natural
products. Beilstein J. Org. Chem. 2013, 9, 2048-2078. (b) Belliotti, T.
R.; Brink, W. A.; Kesten, S. R.; Rubin, J. R.; Wustrow, D. J.; Zoski,
K. T.; Whetzel, S. Z.; Corbin, A. E.; Pugsley, T. A.; Heffner, T. G.;
Wise, L. D. Isoindolinone enantiomers having affinity for the dopa-
mine D4 receptor. Bioorg. Med. Chem. Lett. 1998, 8, 1499-1502. (c)
Hudlicky, T.; Rinner, U.; Gonzalez, D.; Akgun, H.; Schilling, S.;
Siengalewicz, P.; Martinot, T. A.; Pettit, G. R. Total Synthesis and
Biological Evaluation of Amaryllidaceae Alkaloids:ꢀ Narciclasine,
ent-7-Deoxypancratistatin, Regioisomer of 7-Deoxypancratistatin,
10b-epi-Deoxypancratistatin, and Truncated Derivatives. J. Org.
Chem. 2002, 67, 8726-8743.
(7) For selected examples see on construction of chiral isoindo-
linones and isoquinolones: (a) Ye, B.-H.; Cramer, N. Asymmetric
Synthesis of Isoindolones by Chiral Cyclopentadienyl-Rhodium(III)-
Catalyzed C−H Functionalizations. Angew. Chem. Int. Ed. 2014, 53,
7896-7899. (b) Li, T.; Zhou, C.; Yan, X.-Q.; Wang, J. Solvent-
Dependent Asymmetric Synthesis of Alkynyl and Monofluoroalkenyl
Isoindolinones by CpRhIII-Catalyzed C−H Activation. Angew. Chem.
Int. Ed. 2018, 57, 4048-4052. (c) Nishimura, T.; Nagamoto, M.; Ebe,
Y.; Hayashi, T. Enantioselective [3+2] annulation via C−H activation
between cyclic N-acyl ketimines and 1,3-dienes catalyzed by iridi-
um/chiral diene complexes. Chem. Sci. 2013, 4, 4499-4504. (d) Aus-
tin, K. A. B.; Herdtweck, E.; Bach, T. Intramolecular [2+2] Photocy-
cloaddition of Substituted Isoquinolones: Enantioselectivity and Ki-
netic Resolution Induced by a Chiral Template. Angew. Chem. Int. Ed.
2011, 50, 8416-8419. (e) Deng, L.; Xu, T.; Li, H.-B.; Dong, G.-B.
Enantioselective Rh-Catalyzed Carboacylation of C═N Bonds via C-
C Activation of Benzocyclobutenones. J. Am. Chem. Soc. 2016, 138,
369-374. (f) Guo, S.-M.; Xie, Y.-J.; Hu, X.-Q.; Xia, C.-G.; Huang,
H.-M. Diastereo- and Enantioselective Catalytic Tandem Michael
Addition/Mannich Reaction: Access to Chiral Isoindolinones and
Azetidines with Multiple Stereocenters. Angew. Chem. Int. Ed. 2010,
49, 2728-2731.
(12) A leading example for enantioselective desymmetric C−H ac-
tivation of doubly benzylic amine see: Shi, H.; Herron, A. N.; Shao,
Y.; Shao, Q.; Yu, J.-Q. Enantioselective remote meta-C–H arylation
and alkylation via a chiral transient mediator. Nature 2018, 558, 581–
585.
(13) (a) Cheng, G.-J.; Chen, P.; Sun, T.-Y.; Zhang, X.-H., Yu, J.-Q.;
Wu, Y.-D. A Combined IM-MS/DFT Study on [Pd(MPAA)]-
Catalyzed Enantioselective C−H Activation: Relay of Chirality
through a Rigid Framework. Chem. Eur. J. 2015, 21, 11180-11188. (b)
Haines, B. E.; Yu, J.-Q.; Musaev, D. G. Enantioselectivity Model for
Pd-Catalyzed C−H Functionalization Mediated by the Mono-N-
protected Amino Acid (MPAA) Family of Ligands. ACS Catalysis
2017, 7, 4344-4354. (c) Hill, D. E.; Bay, K. L.; Yang, Y.-F.; Plata, R.
E.; Takise, R.; Houk, K. N.; Yu, J.-Q.; Blackmond, D. G. Dynamic
Ligand Exchange as a Mechanistic Probe in Pd-Catalyzed Enantiose-
lective C−H Functionalization Reactions Using Monoprotected Ami-
no Acid Ligands. J. Am. Chem. Soc. 2017, 139, 18500-18503.
(8) (a) Orito, K.; Horibata, A.; Nakamura, T.; Ushito, H.; Nagasaki,
H.; Yuguchi, M.; Yamashita, S.; Tokuda, M. Preparation of Benzolac-
tams by Pd(OAc)2-Catalyzed Direct Aromatic Carbonylation. J. Am.
Chem. Soc. 2004, 126, 14342-14343. For more examples of Pd cata-
lyzed C−H carbonylation of amines see: (b) Taneda, H.; Inamoto, K.;
Kondo, Y. Palladium-Catalyzed Highly Chemoselective Intramolecu-
lar C−H Aminocarbonylation of Phenethylamines to Six-Membered
Benzolactams. Org. Lett. 2016, 18, 2712-2715. (c) Li, W.; Liu, C.;
Zhang, H.; Ye, K.-Y.; Zhang, G.-H.; Zhang, W.-Z.; Duan, Z.-L.; You,
S.-L.; Lei, A.-W. Palladium-Catalyzed Oxidative Carbonylation of N-
Allylamines for the Synthesis of -Lactams. Angew. Chem. Int. Ed.
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