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DOI: 10.1055/s-0036-1590985
Chemoselective Ruthenium-Catalyzed C–O Bond Activation: Orthogonality of Nickel- and Palladium-Catalyzed Reactions for the Synthesis of Polyaryl Fluorenones
Publication History
Received: 05 October 2017
Accepted after revision: 31 October 2017
Publication Date:
14 November 2017 (online)
Published as part of the Cluster C–O Activation
Abstract
Ruthenium-catalyzed C–O bond activation/arylation of methoxy and O-carbamoyl-substituted fluorenones is reported. Established are new reactions of compound 1 (X = H) to aryl (2) and 1,8-diaryl (3) fluorenones. Orthogonal ruthenium-, palladium- and nickel-catalyzed reactions with Suzuki–Miyaura reactions to afford 1,4-diaryl (4) and 1,4,8-triaryl fluorenones (5) are also described. The ready availability of starting methoxy fluorenones by directed ortho and remote metalation tactics confers facility to the presented reactions which may find application in material science areas. DFT calculations have been performed to rationalize the lack of C–H bond reactivity in the ruthenium-catalyzed reaction.
Key words
C–O activation - fluorenone - ruthenium catalysis - nickel catalysis - palladium catalysis - polyarylation - orthogonal cross-couplingSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1590985.
- Supporting Information
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References and Notes
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Antimicrobial activity – Fluostatins A and B:
Anticancer activity:
Anti-HIV activity:
Organic light-emitting diode properties:
Liquid crystal:
Friedel–Crafts ring closure of biarylcarboxylic acid or biarylamide:
Oxidation of fluorenes or fluorenols:
Ring contraction:
For reviews on DoM, see:
For Mg-, Zn-, and Al-amide base-mediated DoM, see:
For review on DoM/cross-coupling/DreM strategies, see:
Dual C–H bond activation:
C–H bond activation:
Oxidative C-H/C-H:
C–H decarboxylative coupling:
Reviews:
COMe functional group activation – Ni-catalyzed Kumada–Tamao–Corriu-type reaction:
Ni-catalyzed Negishi-type reaction:
Ni-catalyzed Mizoroki–Heck-type reaction:
Ru-catalyzed Suzuki-Miyaura type reaction:
Ni-catalyzed Suzuki-Miyaura type reaction:
C–OCONR2 functional group activation – Ni-catalyzed Suzuki–Miyaura type reaction:
Ni-catalyzed Kumada–Tamao–Corriu-type reaction:
Rh-catalyzed Suzuki–Miyaura-type reaction:
C–OCSO2NR2 functional group activation – Ni-catalyzed Kumada–Tamao–Corriu-type reaction:
Ni-catalyzed Suzuki–Miyaura-type reaction:
Aryl C–H activation under Ru catalysis – α-tetralones and 1-benzosuberones:
Anthraquinones:
1-Indanone derivatives are reported to be unreactive under Pd catalysis:
Acetophenones:
Compound 1d has been previously prepared by a ten-step route: