ACS Catalysis
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2015, 7, 863-870. (c) Cheng, H.-G.; Chen, S.; Chen, R.; Zhou, Q., Palladium(II)‐Initiated Catellani‐Type Reactions. Angew. Chem. Int. Ed. 2019,
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(3) (a) Catellani, M.; Motti, E.; Della Ca', N., Catalytic Sequential Reactions Involving Palladacycle-Directed Aryl Coupling Steps. Acc. Chem.
Res. 2008, 41, 1512-1522. (b) Della Ca', N.; Fontana, M.; Motti, E.; Catellani, M., Pd/Norbornene: A Winning Combination for Selective Aromatic
Functionalization via C–H Bond Activation. Acc. Chem. Res. 2016, 49, 1389-1400.
(4) For recent reviews about Pd-catalyzed C–H functionalization, see: (a) 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. (b) 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. (c)
Dey, A.; Agasti, S.; Maiti, D., Palladium Catalysed meta-C–H Functionalization Reactions. Org. Biomol. Chem. 2016, 14, 5440-5453. (d)
Ackermann, L., Carboxylate-Assisted Transition-Metal-Catalyzed C–H Bond Functionalizations: Mechanism and Scope. Chem. Rev. 2011, 111,
1315-1345. (e) Lyons, T. W.; Sanford, M. S., Palladium-Catalyzed Ligand-Directed C–H Functionalization Reactions. Chem. Rev. 2010, 110, 1147-
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(5) For 1:1 coupling of aryl halides and NBE derivatives, see: (a) Catellani, M.; Chiusoli, G. P.; Ricotti, S., A New Palladium-Catalyzed Synthesis
of 1,2,3,4,4a,8b-Hexahydro-1,4-methanobiphenylenes and 2-Phenylbicyclo[2.2.1]hept-2-enes. J. Organomet. Chem. 1985, 296, C11-C15. (b)
Catellani, M.; Ferioli, L., An Improved Synthesis of 1,4-cis,exo-Hexa- or Tetrahydromethano- or -ethanobiphenylene Derivatives Catalyzed by
Palladium Complexes. Synthesis 1996, 1996, 769-772. (c) Hulcoop, D. G.; Lautens, M., Palladium-Catalyzed Annulation of Aryl Heterocycles with
Strained Alkenes. Org. Lett. 2007, 9, 1761-1764. (d) Chai, D. I.; Thansandote, P.; Lautens, M., Mechanistic Studies of Pd-Catalyzed Regioselective
Aryl C–H Bond Functionalization with Strained Alkenes: Origin of Regioselectivity. Chem.–Eur. J. 2011, 17, 8175-8188. (e) Liu, S.; Jin, Z.; Teo,
Y. C.; Xia, Y., Efficient Synthesis of Rigid Ladder Polymers via Palladium Catalyzed Annulation. J. Am. Chem. Soc. 2014, 136, 17434-17437. (f)
Lai, H. W. H.; Teo, Y. C.; Xia, Y., Functionalized Rigid Ladder Polymers from Catalytic Arene-Norbornene Annulation Polymerization. ACS Macro
Lett. 2017, 6, 1357-1361. (g) Abdulhamid, M. A.; Lai, H. W. H.; Wang, Y.; Jin, Z.; Teo, Y. C.; Ma, X.; Pinnau, I.; Xia, Y., Microporous Polyimides
from Ladder Diamines Synthesized by Facile Catalytic Arene–Norbornene Annulation as High-Performance Membranes for Gas Separation. Chem.
Mater. 2019, 31, 1767-1774. For 1:1 coupling of aryl halides and oxa(NBE) derivatives, see: (h) Jin, Z.; Teo, Y. C.; Zulaybar, N. G.; Smith, M. D.;
Xia, Y., Streamlined Synthesis of Polycyclic Conjugated Hydrocarbons Containing Cyclobutadienoids via C–H Activated Annulation and
Aromatization. J. Am. Chem. Soc. 2017, 139, 1806-1809. (i) Jin, Z.; Teo, Y. C.; Teat, S. J.; Xia, Y., Regioselective Synthesis of [3]Naphthylenes
and Tuning of Their Antiaromaticity. J. Am. Chem. Soc. 2017, 139, 15933-15939.
(6) For three-component coupling reactions with NBE derivatives, see: (a) Fan, L.; Liu, J.; Bai, L.; Wang, Y.; Luan, X., Rapid Assembly of
Diversely Functionalized Spiroindenes by a Three-Component Palladium-Catalyzed C−H Amination/Phenol Dearomatization Domino Reaction.
Angew. Chem. Int. Ed. 2017, 56, 14257-14261. (b) Fu, W. C.; Wang, Z.; Chan, W. T. K.; Lin, Z.; Kwong, F. Y., Regioselective Synthesis of
Polycyclic and Heptagon-embedded Aromatic Compounds through a Versatile π-Extension of Aryl Halides. Angew. Chem. Int. Ed. 2017, 56, 7166-
7170. (c) Cheng, M.; Yan, J.; Hu, F.; Chen, H.; Hu, Y., Palladium-Catalyzed Cascade Reactions of 3-Iodochromones with Aryl Iodides and
Norbornadiene Leading to Annulated Xanthones. Chem. Sci. 2013, 4, 526-530. (d) DellaꢀCa', N.; Maestri, G.; Malacria, M.; Derat, E.; Catellani, M.,
Palladium-Catalyzed Reaction of Aryl Iodides with ortho-Bromoanilines and Norbornene/Norbornadiene: Unexpected Formation of Dibenzoazepine
Derivatives. Angew. Chem. Int. Ed. 2011, 50, 12257-12261. (e) Bhuvaneswari, S.; Jeganmohan, M.; Cheng, C.-H., Carbocyclization of Aromatic
Iodides, Bicyclic Alkenes, and Benzynes Involving a Palladium-Catalyzed C–H Bond Activation as a Key Step. Org. Lett. 2006, 8, 5581-5584.
(7) (a) Klärner, F.-G.; Schrader, T., Aromatic Interactions by Molecular Tweezers and Clips in Chemical and Biological Systems. Acc. Chem. Res.
2013, 46, 967-978. (b) Stockdale, T. P.; Williams, C. M., Pharmaceuticals that Contain Polycyclic Hydrocarbon Scaffolds. Chem. Soc. Rev. 2015,
44, 7737-7763. (c) Defieber, C.; Grützmacher, H.; Carreira, E. M., Chiral Olefins as Steering Ligands in Asymmetric Catalysis. Angew. Chem. Int.
Ed. 2008, 47, 4482-4502. (d) Saito, M.; Shinokubo, H.; Sakurai, H., Figuration of Bowl-Shaped π-Conjugated Molecules: Properties and Functions.
Mater. Chem. Front. 2018, 2, 635-661.
(8) For selected recent examples, see: (a) Wang, X.-C.; Gong, W.; Fang, L.-Z.; Zhu, R.-Y.; Li, S.; Engle, K. M.; Yu, J.-Q., Ligand-Enabled
meta-C–H Activation Using a Transient Mediator. Nature 2015, 519, 334-338. (b) Shi, G.; Shao, C.; Ma, X.; Gu, Y.; Zhang, Y., Pd(II)-Catalyzed
Catellani-Type Domino Reaction Utilizing Arylboronic Acids as Substrates. ACS Catal. 2018, 8, 3775-3779. (c) Li, R.; Liu, F.; Dong, G., Redox-
Neutral ortho Functionalization of Aryl Boroxines via Palladium/Norbornene Cooperative Catalysis. Chem 2019, 5, 929-939.
(9) Wang, J.; Li, R.; Dong, Z.; Liu, P.; Dong, G., Complementary Site-Selectivity in Arene Functionalization Enabled by Overcoming the ortho
Constraint in Palladium/Norbornene Catalysis. Nat. Chem. 2018, 10, 866-872.
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(10) (a) Dong, Z.; Lu, G.; Wang, J.; Liu, P.; Dong, G., Modular ipso/ortho Difunctionalization of Aryl Bromides via Palladium/Norbornene
Cooperative Catalysis. J. Am. Chem. Soc. 2018, 140, 8551-8562. (b) Casnati, A.; Fontana, M.; Coruzzi, G.; Aresta, B. M.; Corriero, N.; Maggi, R.;
Maestri, G.; Motti, E.; DellaꢀCa', N., Enhancing Reactivity and Selectivity of Aryl Bromides: A Complementary Approach to Dibenzo[b,f]azepine
Derivatives. ChemCatChem 2018, 10, 4346-4352.
(11) (a) Wolfe, J. P.; Li, J. J. Palladium in Heterocyclic Chemistry; Li, J. J.; Gribble, G. Eds. Elsevier, Oxford, 2007; pp. 1-3. (b) Bheeter, C. B.;
Chen, L.; Soule, J.-F.; Doucet, H., Regioselectivity in Palladium-Catalysed Direct Arylation of 5-Membered Ring Heteroaromatics. Catal. Sci.
Technol. 2016, 6, 2005-2049. (c) Yang, Y.; Lan, J.; You, J., Oxidative C–H/C–H Coupling Reactions between Two (Hetero)arenes. Chem. Rev.
2017, 117, 8787-8863.
(12) Mitsudo, K.; Thansandote, P.; Wilhelm, T.; Mariampillai, B.; Lautens, M., Selectively Substituted Thiophenes and Indoles by a Tandem
Palladium-Catalyzed Multicomponent Reaction. Org. Lett. 2006, 8, 3939-3942.
(13) For Pd/NBE cooperative catalysis of parent heterocycles: (a) Li, R.; Zhou, Y.; Xu, X.; Dong, G., Direct Vicinal Difunctionalization of
Thiophenes Enabled by the Palladium/Norbornene Cooperative Catalysis. J. Am. Chem. Soc. 2019, 141, 18958-18963. (b) Jiao, L.; Bach, T.,
Palladium-Catalyzed Direct C–H Alkylation of Electron-Deficient Pyrrole Derivatives. Angew. Chem. Int. Ed. 2013, 52, 6080-6083. (c) Jiao, L.;
Herdtweck, E.; Bach, T., Pd(II)-Catalyzed Regioselective 2-Alkylation of Indoles via a Norbornene-Mediated C–H Activation: Mechanism and
Applications. J. Am. Chem. Soc. 2012, 134, 14563-14572. (d) Jiao, L.; Bach, T., Palladium-Catalyzed Direct 2-Alkylation of Indoles by Norbornene-
Mediated Regioselective Cascade C–H Activation. J. Am. Chem. Soc. 2011, 133, 12990-12993.
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