Regiodivergent Access to 2- or 3-Substituted Indanones: Catalyst-Controlled Carboacylation via C–C Bond Activation

Shao, Pengcheng P.; Yu, Tao; Lu, Hong; Xu, Peng‐Fei; Wei, He

doi:10.31635/ccschem.020.202000448

Cited by 12 publications

(9 citation statements)

References 64 publications

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“…Particularly, the TM-catalyzed alkene carboacylation reactions provide easy access to ketones, which are key structural motifs in many natural products 5 , 6 . The intramolecular carboacylation under TM catalysis has been well established, including carboacylation with acylquinolines 7 – 10 , reactions of alkenes tethered with ring-strained cyclobutanones 11 – 13 , unstrained ketones 14 , and amides 15 , etc. However, the intermolecular TM-catalyzed carboacylation has been far less developed.…”

Section: Introductionmentioning

confidence: 99%

Photoredox cooperative N-heterocyclic carbene/palladium-catalysed alkylacylation of alkenes

et al. 2022

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Three-component carboacylation of simple alkenes with readily available reagents is challenging. Transition metal-catalysed intermolecular carboacylation works for alkenes with strained ring or directing groups. Herein, we develop a photoredox cooperative N-heterocyclic carbene/Pd-catalysed alkylacylation of simple alkenes with aldehydes and unactivated alkyl halides to provide ketones in good yields. This multicomponent coupling reaction features a wide scope of alkenes, broad functional group compatibility and free of exogenous photosensitizer or external reductant. In addition, a series of chlorinated cyclopropanes with one or two vicinal quaternary carbons is obtained when chloroform or carbon tetrachloride is used as the alkyl halide. The reaction involves the alkyl radicals from halides and the ketyl radicals from aldehydes under photoredox cooperative N-heterocyclic carbene/Pd catalysis.

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Section: Introductionmentioning

confidence: 99%

Photoredox cooperative N-heterocyclic carbene/palladium-catalysed alkylacylation of alkenes

et al. 2022

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“…This method provides an alternative approach to access substituted 1-indanones from available 2′-vinylaryl ketones without generating stoichiometric byproducts. When this work was in progress, a mechanistically related transformation was reported by Wei and co-workers, which relies on the use of permanently installed directing groups. To the best of our knowledge, the use of simple unstrained ketones has not been reported for such a transformation.…”

mentioning

confidence: 99%

Intramolecular One-Carbon Homologation of Unstrained Ketones via C–C Activation-Enabled 1,1-Insertion of Alkenes

Huang

Zhang

et al. 2022

Org. Lett.

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Here, we describe the development of a Rhcatalyzed intramolecular one-carbon homologation of unstrained aryl ketones through a formal 1,1-insertion process of olefins, enabled by temporary directing group (TDG)-aided C−C activation. The reaction provides a distinct approach to access various substituted 1-indanones. Computational mechanistic studies reveal that the formal 1,1-insertion is realized by a selective C(sp 2 )−C(sp 3 ) activation and turnover limiting 2,1-insertion into the alkene, followed by a facile β-H elimination and reinsertion process.

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“…For unstrained ketones [27][28][29][30][31][32] , the most common strategy involves using directing groups to form of a stable chelate (Fig. 1c) [33][34][35][36][37][38][39][40] . Although effective, the use of directing groups complicates the overall synthesis and limits the scope of the accessible products.…”

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confidence: 99%

Rapid syntheses of N-fused heterocycles via acyl-transfer in heteroaryl ketones

et al. 2022

Nat Commun

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The wide-ranging potencies of bioactive N-fused heterocycles inspire the development of synthetic transformations that simplify preparation of their complex, diverse structural motifs. Heteroaryl ketones are ubiquitous, readily available, and inexpensive molecular scaffolds, and are thus synthetically appealing as precursors in preparing N-fused heterocycles via intramolecular acyl-transfer. To best of our knowledge, acyl-transfer of unstrained heteroaryl ketones remains to be demonstrated. Here, we show an acyl transfer-annulation to convert heteroaryl ketones to N-fused heterocycles. Driven via aromatisation, the acyl of a heteroaryl ketone can be transferred from the carbon to the nitrogen of the corresponding heterocycle. The reaction commences with the spiroannulation of a heteroaryl ketone and an alkyl bromide, with the resulting spirocyclic intermediate undergoing aromatisation-driven intramolecular acyl transfer. The reaction conditions are optimised, with the reaction exhibiting a broad substrate scope in terms of the ketone and alkyl bromide. The utility of this protocol is further demonstrated via application to complex natural products and drug derivatives to yield heavily functionalised N-fused heterocycles.

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Regiodivergent Access to 2- or 3-Substituted Indanones: Catalyst-Controlled Carboacylation via C–C Bond Activation

Cited by 12 publications

References 64 publications

Photoredox cooperative N-heterocyclic carbene/palladium-catalysed alkylacylation of alkenes

Photoredox cooperative N-heterocyclic carbene/palladium-catalysed alkylacylation of alkenes

Intramolecular One-Carbon Homologation of Unstrained Ketones via C–C Activation-Enabled 1,1-Insertion of Alkenes

Rapid syntheses of N-fused heterocycles via acyl-transfer in heteroaryl ketones

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