C-H Activation
C–H Activation and related reactions revolutionized the way organic molecules are made and allow a more efficient use of earth‘s natural resources. In the last couple of years, many challenges like extreme conditions or low selectivities have been tackled. However, most methods rely on coordinating directing groups. We strive to render C–H activation more practical by developing new strategies avoiding the use of synthetically often unfavorable directing groups. In this regard, our group recently focused on the activation of allylic C–H bonds allowing the selective functionalization of C(sp3)–H bonds using Rh(III) and Ir(III) catalysis.[1-3] Using the power of precious metals, a myriad of transformations has been developed. However, these highly reactive catalysts are not only of high cost but also often toxic. In our opinion, the use of earth-abundant transition metals is a powerful tool to render these methods more sustainable. In this regard, our group developed various MnI-catalyzed methods for the functionalization of heterocycles.[4,5]
[1] A. Lerchen, T. Knecht, M. Koy, J. B. Ernst, K. Bergander, F. Glorius, Angew. Chem. Int. Ed. 2018, 57, 15248. [2] T. Knecht, T. Pinkert, T. Dalton, A. Lerchen, F. Glorius, ACS Catal. 2019, 9, 1253. [3] T. Knecht, S. Mondal, J. H. Ye, M. Das, F. Glorius, Angew. Chem. Int. Ed. 2019, 58, 7117. [4] Q. Lu, S. Greßies, S. Cembellín, F. J. R. Klauck, C. G. Daniliuc, F. Glorius, Angew. Chem. Int. Ed. 2017, 56, 12778. [5] C. Zhu, J. L. Schwarz, S. Cembellín, S. Greßies, F. Glorius, Angew. Chem. Int. Ed. 2018, 57, 437.
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G. Tan,§ I. Maisuls,§ F. Strieth-Kalthoff, X. Zhang, C. Daniliuc, C. A. Strassert*, F. Glorius,*
AIE-Active Difluoroboron Complexes with N,O-Bidentate Ligands: Rapid Construction by Copper-Catalyzed C−H Activation,
Adv. Sci. 2021, 8, 202101814 (open access).
§ These authors contributed equally.
T. Pinkert, M. Das, M. L. Schrader, F. Glorius,
The Use of Strain-Release for the Diastereoselective Construction of Quaternary Carbon Centers,
J. Am. Chem. Soc. 2021, 143, 7648-7654.
G. Tan, M. Das, I. Maisuls, C. A. Strassert, Frank Glorius,
Rhodium-Catalyzed Dealkenylative Arylation of Alkenes with Arylboronic Compounds,
Angew. Chem. Int. Ed. 2021, 60, 15650-15655; Angew. Chem. 2021, 133, 15780-15785.
T. Dalton,§ S. Greßies,§ M. Das, M. Niehues,§§ M. L. Schrader,§§ C. Gutheil,§§ B. J. Ravoo, F. Glorius,
Silver-Catalysed Hydroarylation of Highly Substituted Styrenes,
Angew. Chem. Int. Ed. 2021, 60, 8537-8541; Angew. Chem. 2021, 133, 8616-8623.
§,§§ These authors contributed equally.
S. Mondal, T. Pinkert, C. G. Daniliuc, F. Glorius,
Regioselective and Redox-Neutral Cp*IrIII-Catalyzed Allylic C–H Alkynylation,
Angew. Chem. Int. Ed. 2021, 60, 5688-5672; Angew. Chem. 2021, 133, 5752-5756.
T. Dalton, T. Faber, F. Glorius,
C-H Activation: towards sustainability and applications,
ACS Cent. Sci. 2021, 7, 245-261.
G. Tan, M. L. Schrader, C. Daniliuc, F. Strieth-Kalthoff, F. Glorius,
C-H Activation Based Copper-Catalyzed One-Shot Synthesis of Organic Difluoroboron Complexes,
Angew. Chem. Int. Ed. 2020, 59, 21541-21545; Angew. Chem. 2020, 132, 21725-21729.
S. Cembellín, T. Dalton, T. Pinkert, F. Schäfers, F. Glorius,
Highly Selective Synthesis of 1,3-Enynes, Pyrroles, and Furans by Manganese(I)-Catalyzed C–H Activation,
ACS Catalysis 2020, 10, 197-202.
T. Pinkert, T. Wegner, S. Mondal, F. Glorius,
Intermolecular 1,4–Carboamination of Conjugated Dienes Enabled by Cp*RhIII‐Catalyzed C–H Activation,
Angew. Chem. Int. Ed. 2019, 58, 15041-15045; Angew. Chem. 2019, 131, 15183-15187.
T. Knecht,§ S. Mondal,§ J.-H. Ye, M. Das, F. Glorius,
Intermolecular, Branch-Selective and Redox-Neutral Cp*IrIII-Catalyzed Allylic C–H Amidation,
Angew. Chem. Int. Ed. 2019, 58, 7117-7121; Angew. Chem. 2019, 131, 7191-7195.
§ Both authors contributed equally.
A. Lerchen, T. Knecht, M. Koy, J. B. Ernst, K. Bergander, C. G. Daniliuc, F. Glorius,
Non-Directed Cross-Dehydrogenative (Hetero)arylation of Allylic C(sp3)–H bonds enabled by C–H activation,
Angew. Chem. Int. Ed. 2018, 57, 15248-15253; Angew. Chem. 2018, 130, 15468-15472.
S. Greßies, F. Klauck, J. H. Kim, C. Daniliuc, F. Glorius,
Ligand-Enabled Enantioselective Csp3-H Activation of Tetrahydroquinolines and Saturated Aza-Heterocycles by Rh(I),
Angew. Chem. Int. Ed. 2018, 57, 9950-9954; Angew. Chem. 2018, 130, 10098-10102.
Q. Lu, S. Mondal, S. Cembellín, F. Glorius,
Mn(I)/Ag(I) Relay Catalysis: Traceless Diazo-Assisted C(sp2)–H/C(sp3)–H Coupling to β-(Hetero)Aryl/Alkenyl Ketones,
Angew. Chem. Int. Ed. 2018, 57, 10732-10736; Angew. Chem. 2018, 130, 10892-10896.
X. Wang, Y. Li, T. Knecht, C. G. Daniliuc, K. Houk,* F. Glorius,*
Unprecedented Dearomatized Spirocyclopropane in a Sequential Rh(III)-catalyzed C-H Activation and Rearrangement Reaction,
Angew. Chem. Int. Ed. 2018, 57, 5520-5524; Angew. Chem. 2018, 130, 5618-5622.
X. Wang, A. Lerchen, C. G. Daniliuc, F. Glorius,
Efficient Synthesis of Arylated Furans Enabled by a Sequential Rh-catalyzed Arylation and Cycloisomerization of Cyclopropenes,
Angew. Chem. Int. Ed. 2018, 57, 1712-1716; Angew. Chem. 2018, 130, 1728-1732.
T. Gensch, M. James, T. Dalton, F. Glorius,
Increasing Catalyst Efficiency in C−H Activation Catalysis,
Angew. Chem. Int. Ed. 2018, 57, 2296-2306; Angew. Chem. 2018, 130, 2318-2328.
Q. Lu, S. Cembellín Santos, S. Greßies, S. Singha, C. Daniliuc, F. Glorius,
Manganese(I)-Catalyzed C-H (2-indolyl)methylation: Expedient Access to Diheteroarylmethanes,
Angew. Chem. Int. Ed. 2018, 57, 1399-1403; Angew. Chem. 2018, 130, 1413-1417.
S. Vásquez-Céspedes, X. Wang, F. Glorius,
Plausible Rh(V) Intermediates in Catalytic C−H Activation Reactions,
ACS Catal. 2018, 8, 242-257.
C. Zhu, J. L. Schwarz, S. Cembellín, S. Greßies, F. Glorius,
Highly Selective Manganese(I)/Lewis Acid Cocatalyzed Direct C−H Propargylation Using Bromoallenes,
Angew. Chem. Int. Ed. 2018, 57, 437-441; Angew. Chem. 2018, 130, 445-449.
Q. Lu§, S. Greßies§, S. Cembellín, F. J. R. Klauck, C. G. Daniliuc, F. Glorius,
Redox-Neutral Manganese(I)-Catalyzed C–H Activation: Traceless Directing Group Enabled Regioselective Annulation,
Angew. Chem. Int. Ed. 2017, 56, 12778-12782; Angew. Chem. 2017, 129, 12954-12958.
§ Both authors contributed equally.
A. Lerchen, T. Knecht, M. Koy, C. G. Daniliuc, F. Glorius,
A General Cp*Co(III)-Catalyzed Intramolecular C–H Activation Approach for the Efficient Total Syntheses of Aromathecin, Protoberberine and Tylophora Alkaloids,
Chem. Eur. J. 2017, 23, 12149-12152.
X. Wang, T. Gensch, A. Lerchen, C. G. Daniliuc, F. Glorius,
Cp*Rh(III)/Bicyclic Olefin Cocatalyzed C−H Bond Amidation by Intramolecular Amide Transfer,
J. Am. Chem. Soc. 2017, 139, 6506-6512.
Q. Lu, S. Greßies, F. J. R. Klauck, F. Glorius,
Manganese(I)-Catalyzed Regioselective C–H Allenylation: Direct Access to 2-Allenylindoles,
Angew. Chem. Int. Ed. 2017, 56, 6660-6664; Angew. Chem. 2017, 129, 6760-6764.
Q. Lu, F. J. R. Klauck, F. Glorius,
Manganese-Catalyzed Allylation via Sequential C–H and C–C/C–Het Bond Activation,
Chem. Sci. 2017, 8, 3379-3383.
X. Wang, A. Lerchen, T. Gensch, T. Knecht, C. G. Daniliuc, F. Glorius,
Combination of Cp*RhIII-Catalyzed C-H Activation and a Wagner–Meerwein-Type Rearrangement,
Angew. Chem. Int. Ed. 2017, 56, 1381-1384; Angew. Chem. 2017, 129, 1401-1405.
A. Lerchen, T. Knecht, C. G. Daniliuc, F. Glorius,
Unnatural Amino Acid Synthesis Enabled by the Regioselective Cobalt(III)-Catalyzed Intermolecular Carboamination of Alkenes,
Angew. Chem. Int. Ed. 2016, 55, 15166-15170; Angew. Chem. 2016, 128, 15391-15395.
T. Gensch, F. J. R. Klauck, F. Glorius,
Cobalt-Catalyzed C−H Thiolation through Dehydrogenative Cross-Coupling,
Angew. Chem. Int. Ed. 2016, 55, 11287-11291; Angew. Chem. 2016, 128, 11457-11461.
T. Gensch, M. N. Hopkinson, F. Glorius,* J. Wencel-Delord,*
Mild metal-catalyzed C–H activation: examples and concepts,
Chem. Soc. Rev. 2016, 45, 2900-2936.
J. H. Kim, S. Greßies, F. Glorius,
Cooperative Lewis Acid/ Cp*Co(III)-Catalyzed C–H Bond Activation for the Synthesis of Isoquinolin-3-ones,
Angew. Chem. Int. Ed. 2016, 55, 5577-5581; Angew. Chem. 2016, 128, 5667-5671.
A. Lerchen, S. Vásquez-Céspedes, F. Glorius,
Cobalt(III)-catalyzed redox-neutral synthesis of unprotected indoles featuring an N–N bond cleavage,
Angew. Chem. Int. Ed. 2016, 55, 3208-3211; Angew. Chem. 2016, 128, 3261-3265.
J. H. Kim, T. Gensch, D. Zhao, L. Stegemann, C. A. Strassert,* F. Glorius,*
Rh(III)-Catalyzed C-H Activation with Pyridotriazoles: Direct Access to Fluorophores for Metal-Ion Detection,
Angew. Chem. Int. Ed. 2015, 54, 10975–10979; Angew. Chem. 2015, 127, 11126–11130.
X. Wang,§ D.-G. Yu,§ F. Glorius,
Cp*Rh(III)-Catalyzed Arylation of sp3 C−H Bonds,
Angew. Chem. Int. Ed. 2015, 54, 10280-10283;Angew. Chem. 2015, 127, 10419-10422.
§ Both authors contributed equally.
S. Vásquez-Céspedes§, A. Ferry§, L. Candish, F. Glorius,
Heterogeneously Catalyzed Direct C-H Thiolation of Heteroarenes,
Angew. Chem. Int. Ed. 201554, 5772-5776; Angew. Chem. 2015, 127, 5864-5868.
§ Both authors contributed equally.
N. Schröder, F. Lied, F. Glorius,
Dual role of Rh(III)-catalyst enables regioselective halogenation of (electron-rich) heterocycles,
J. Am. Chem. Soc. 2015, 137, 1448-1451.
D. Zhao*§, J. H. Kim§, L. Stegemann, C. A. Strassert, F. Glorius,*
Cobalt(III)-Catalyzed Directed CH Coupling with Diazo Compounds: Straightforward Access towards Extended π-Systems,
Angew. Chem. Int. Ed. 2015, 54, 4508-4511; Angew. Chem. 2015, 127, 4591-4594.
§ Both authors contributed equally.
D. Zhao,§ S. Vásquez-Céspedes,§ F. Glorius,
Rhodium(III)-Catalyzed Cyclative Capture Approach to Diverse 1-Aminoindoline Derivatives at Room Temperature,
Angew. Chem. Int. Ed. 2015, 54, 1657-1661; Angew. Chem. 2015, 127, 1677-1681.
§ Both authors contributed equally.