Remote C(sp<sup>3</sup>)–H activation: palladium-catalyzed intermolecular arylation and alkynylation with organolithiums and terminal alkynes

Chen, Peng; Wang, Zhiyong; Wang, Jiaxin; Peng, Xiao‐Shui; Wong, H. N. C.

doi:10.1039/d2qo00584k

Cited by 4 publications

(1 citation statement)

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“…Very recently, the efficient remote Csp 3 –H activation reactions involving the direct Pd-catalysed cross-coupling of aryllithium reagents with terminal alkynes were disclosed by Wong, Peng and co-workers ( Scheme 8 ). 24 This strategy showed a broad functional group tolerance with excellent regioselectivities, affording the desired products up to 98% yield. It should be noted that the sterically hindered alkynes proceeded smoothly under optimal conditions.…”

Section: Organo-alkali Metal Reagents In the Formation Of Carbon–carb...mentioning

confidence: 96%

Sustainable and practical formation of carbon–carbon and carbon–heteroatom bonds employing organo-alkali metal reagents

et al. 2023

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Section: Organo-alkali Metal Reagents In the Formation Of Carbon–carb...mentioning

confidence: 96%

Sustainable and practical formation of carbon–carbon and carbon–heteroatom bonds employing organo-alkali metal reagents

et al. 2023

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Advances in Palladium-Catalyzed C(sp³)–H Functionalization: The Role of Traceless Directing Groups

Sadeghi

2024

ACS Catal.

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Selective functionalization of a specific C(sp 3 )−H bond remains an open challenge in synthetic chemistry. One common strategy employed by chemists to address this challenge is the use of directing groups to select and break a particular C(sp 3 )−H bond. There are various types of directing groups, classified based on their roles during the reaction, such as removable, nonremovable, transient, and traceless directing groups (TDGs). Among them, TDGs including −I, −Br, −OTf, −ONf, and −COOH have been explored for C(sp 3 )−H functionalization using different catalysts. Palladium is one of the widely used catalysts for the functionalization of C(sp 3 )−H via TDGs, and Pd(OAc) 2 is the most commonly used palladium complex in these reactions. Palladium can form a palladacycle intermediate (usually a five-membered ring) to facilitate the activation and functionalization of target C(sp 3 )−H bonds, which is often crucial in these transformations. Literature review indicates that palladium-catalyzed C−H functionalization via TDGs has been successfully applied for the formation of several bonds, including C− C, C−N, C−B, and C−P bonds. This Review discusses palladium-catalyzed protocols, in which a TDG is employed to guide the palladium catalyst in activating and functionalizing desired C(sp 3 )−H bonds.

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1,4-Pd Migration-Enabled Synthesis of Fused 4-Membered Rings

Tsitopoulou,

Clemenceau,

Thesmar

et al. 2024

J. Am. Chem. Soc.

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1,4-Palladium migration has been widely used for the functionalization of remote C−H bonds. However, this mechanism has been limited to aryl halide precursors. This work reports an unprecedented Pd 0 -catalyzed cyclobutanation protocol producing valuable fused cyclobutanes starting from cycloalkenyl (pseudo)halides. This reaction takes place via alkenyl-to-alkyl 1,4-Pd migration, followed by intramolecular Heck coupling. The method performs best with cyclohexenyl precursors, giving access to a variety of substituted bicyclo[4,2,0]octenes. Reactants containing an N-methyl or methoxy group give rise to fused azetidines or oxetanes, respectively, via the same mechanism. Kinetic and deuterium-labeling studies point to a rate-limiting C(sp 3 )−H activation step. * sı Supporting InformationThe Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.4c04701.Full optimization tables, crystallographic data, experimental procedures, and spectral data (PDF)

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Remote C(sp³)–H activation: palladium-catalyzed intermolecular arylation and alkynylation with organolithiums and terminal alkynes

Abstract: 1,4-Palladium shift is regarded as one of the solutions towards the challenging remote C(sp3)−H activation. Herein we report two efficient remote C(sp3)−H activation protocols involving palladium-catalyzed C(sp3)−C(sp2) and C(sp3)−C(sp) cross-coupling...

Cited by 4 publications

References 82 publications

Sustainable and practical formation of carbon–carbon and carbon–heteroatom bonds employing organo-alkali metal reagents

Sustainable and practical formation of carbon–carbon and carbon–heteroatom bonds employing organo-alkali metal reagents

Advances in Palladium-Catalyzed C(sp³)–H Functionalization: The Role of Traceless Directing Groups

1,4-Pd Migration-Enabled Synthesis of Fused 4-Membered Rings

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Remote C(sp3)–H activation: palladium-catalyzed intermolecular arylation and alkynylation with organolithiums and terminal alkynes

Abstract: 1,4-Palladium shift is regarded as one of the solutions towards the challenging remote C(sp3)−H activation. Herein we report two efficient remote C(sp3)−H activation protocols involving palladium-catalyzed C(sp3)−C(sp2) and C(sp3)−C(sp) cross-coupling...

Cited by 4 publications

References 82 publications

Sustainable and practical formation of carbon–carbon and carbon–heteroatom bonds employing organo-alkali metal reagents

Sustainable and practical formation of carbon–carbon and carbon–heteroatom bonds employing organo-alkali metal reagents

Advances in Palladium-Catalyzed C(sp3)–H Functionalization: The Role of Traceless Directing Groups

1,4-Pd Migration-Enabled Synthesis of Fused 4-Membered Rings

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Product

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Remote C(sp³)–H activation: palladium-catalyzed intermolecular arylation and alkynylation with organolithiums and terminal alkynes

Advances in Palladium-Catalyzed C(sp³)–H Functionalization: The Role of Traceless Directing Groups