Palladium‐Catalyzed C8‐Arylation of Naphthalenes through C−H Activation: A Combined Experimental and Computational Study

Garrec, Julian; Cordier, Marie; Frison, Gilles; Prévost, Sébastien

doi:10.1002/chem.201903500

Cited by 16 publications

(9 citation statements)

References 79 publications

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“…The complete selectivity observed at C8 rather than at C2 has been explained by the preferred orientation of the DG carbonyl fragment pointing towards the C8-H bond and rationalized using DFT calculations. 72 Similar results were obtained using Weinreb-type amides. Further, the transformation tolerates substitution on the naphthalene platform as well as on the aryl group introduced at position 8.…”

Section: Short Review Syn Thesissupporting

confidence: 67%

C–H Functionalization Strategies in the Naphthalene Series: Site Selections and Functional Diversity

Large

Prim²

2020

Synthesis

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Naphthalene is certainly not a common arene. In contrast to benzene, the bicyclic feature of naphthalene offers multiple differentiable positions and thus a broad diversity of substitution patterns. Naphthalene is a central building block for the construction of elaborated polycyclic architectures with applications in broad domains such as life and materials sciences. As a result, C–H functionalization strategies specially designed for naphthalene substrates have become essential to install valuable substituents on one or both rings towards polysubstituted naphthalenes. This short review provides a focus on uncommon substitution patterns; however, classical ortho C–H activation is not covered.1 Introduction2 C–H Functionalization Using a Directing Group Located at Position 12.1 Functionalization on the Ring Bearing the DG: 1,3-Substitution Pattern2.2 Functionalization on the Ring Bearing the DG: 1,4-Substitution Pattern2.3 Functionalization on the Neighboring Ring: 1,6-, 1,7- and 1,8-Substitution Patterns3 C–H Functionalization Using a Directing Group Located at Position 23.1 Functionalization on the Ring Bearing the DG: 2,4- and 2,1-Substitution Patterns3.2 Miscellaneous Substitution Patterns4 Bis C–H Functionalization4.1 Symmetrical Bisfunctionalization: 1,2,8-Substitution Pattern4.2 Symmetrical Bisfunctionalization: 2,3,1-Substitution Pattern4.2 Unsymmetrical Bisfunctionalization: 2,3,1-Substitution Pattern4.3 Symmetrical Bisfunctionalization: 2,4,8-Substitution Pattern5 Conclusion and Outlook

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Section: Short Review Syn Thesissupporting

confidence: 67%

C–H Functionalization Strategies in the Naphthalene Series: Site Selections and Functional Diversity

Large

Prim²

2020

Synthesis

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“…Intriguingly, when 9-anthracenecarboxaldehyde oxime was used as the substrate, a peri -C–H bond etherification was observed in good yield (Scheme a). − Chiral secondary alcohols are ubiquitous units in various bioactive compounds and natural products, thus the C–H bond etherification with chiral alcohols represents a rapid way to construct important chiral ethers. Indeed, the mechanochemical C–H bond etherification of 1a with enantioenriched 1-phenyl ethyl alcohol (S)- 2s or (R)- 2s took place smoothly to give the corresponding chiral products with no erosion of the chirality (Scheme b).…”

Section: Resultsmentioning

confidence: 99%

Solvent-less Dehydrogenative C–H Etherification with Alcohols Using Mechanochemistry

Zhou

Hao

Mao

et al. 2021

ACS Sustainable Chem. Eng.

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The aromatic C–H bond etherification with alcohols is one of the most atom-efficient ways to construct aryl ethers. However, it often requires a large excess of alcohols as etherification reagents, which limits the substrate scope (especially for the valuable alcohols). Herein, an alternative mechanochemical C–H bond etherification of oximes with diverse primary and secondary alcohols was developed for the first time. Given the solvent-less condition of ball milling technique, the amount of alcohols used in this chemistry has been significantly reduced (1.5–3.0 equiv to the substrates), thus enabling the incorporation of a wide range of alcohols in the C–H bond etherification for the first time. The present mechanochemical protocol enhances the application prospect of the cross dehydrogenative C–H etherification strategy in the late-stage synthesis of complex aromatic ethers.

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“…In regards to C8‐functionalization with carbonyl as weakly coordinating directing group, few works have been reported [14] . Inspired by the work of Xiao and Fu's group on C8‐triflation, [14a] we recently disclosed a palladium‐catalyzed C8‐arylation of naphthalene derivatives (Scheme 1b) [14d] . However, C8‐functionalization of 1‐carbonyl naphthalenes is still under‐studied.…”

Section: Figurementioning

confidence: 99%

Palladium‐Catalyzed C8‐Oxygenation of Naphthalene Derivatives: Direct Access to Naphtholactone Skeleton

Berrou

Prévost

2021

Adv Synth Catal

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Herein, a direct C8‐oxygenation of naphthalene derivatives is described. Different carbonyl groups were used as directing group to deliver corresponding naphthols via a palladium‐catalyzed oxidation reaction using PhI(OAc)2 in a TFA/TFAA mixture. Interestingly, when Weinreb amide was employed as the directing group, the naphtholactone skeleton was directly obtained. This methodology was applied to the synthesis of variously substituted naphtholactones.

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Palladium‐Catalyzed C8‐Arylation of Naphthalenes through C−H Activation: A Combined Experimental and Computational Study

Cited by 16 publications

References 79 publications

C–H Functionalization Strategies in the Naphthalene Series: Site Selections and Functional Diversity

C–H Functionalization Strategies in the Naphthalene Series: Site Selections and Functional Diversity

Solvent-less Dehydrogenative C–H Etherification with Alcohols Using Mechanochemistry

Palladium‐Catalyzed C8‐Oxygenation of Naphthalene Derivatives: Direct Access to Naphtholactone Skeleton

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