Scandium-Catalyzed <i>para</i>-Selective Alkylation of Aromatic Amines with Alkenes

Su, Jianhong; Cai, Yanping; Xu, Xin

doi:10.1021/acs.orglett.9b03451

Cited by 36 publications

(21 citation statements)

References 47 publications

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“…By using norbornene as a transient mediator, Yu’s group demonstrates the catalytic meta -selective alkylation with standard ortho -directing groups (Scheme b) . Moreover, a few examples of arenes bearing functional groups (FGs) including sulfonylarenes, anilines, anilides, amines, phenols, ketones, and aldehydes are also reported for the para -selective alkylation (Scheme c).…”

mentioning

confidence: 99%

Aldehyde as a Traceless Directing Group for Regioselective C–H Alkylation Catalyzed by Rhodium(III) in Air

Chen

et al. 2020

Org. Lett.

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The aromatic aldehyde as a traceless directing group for the regionselective C–H alkylation catalyzed by rhodium(III) under aerobic atmospheric conditions has been developed. The process involves an aldehyde assisted direct addition of C–H bond to unsaturated electrophiles of acrylates or acrylic acids, and the subsequent decarbonylation. A trace amount of water is found to favor the reaction.

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confidence: 99%

Aldehyde as a Traceless Directing Group for Regioselective C–H Alkylation Catalyzed by Rhodium(III) in Air

Chen

et al. 2020

Org. Lett.

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“…It is relatively cheap compared to heavier transition metals, and it is commonly used on catalytic procedures, such as catalyzed polymerization [31,32] and C-C coupling reactions [33,34]. It is also an increasing metal option to develop C-H activation methods, since it can be used as the metallic center of innovative and elaborated complexes [35,36]. Scandium-based catalysts have not been directly applied to the synthesis of known biologically active compounds via C-H activation reactions.…”

Section: Review Scandium-catalyzed C-h Activationmentioning

confidence: 99%

On the application of 3d metals for C–H activation toward bioactive compounds: The key step for the synthesis of silver bullets

Carvalho¹,

Miranda²,

Nunes³

et al. 2021

Beilstein J. Org. Chem.

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Several valuable biologically active molecules can be obtained through C–H activation processes. However, the use of expensive and not readily accessible catalysts complicates the process of pharmacological application of these compounds. A plausible way to overcome this issue is developing and using cheaper, more accessible, and equally effective catalysts. First-row transition (3d) metals have shown to be important catalysts in this matter. This review summarizes the use of 3d metal catalysts in C–H activation processes to obtain potentially (or proved) biologically active compounds.

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“…On a large scale, the C-functionalization of aniline is thus restricted to the methyl group (Scheme ), which limits the possibility of tuning the physicochemical properties of polyurethanes, the biggest market share of aniline . Driven by increasing environmental concerns and associated stringent legislation, the chemical industry is seeking clean technologies to C-functionalize aniline. − In this context, the hydroarylation of alkenes with aniline has become a reaction of interest, as it provides an access to C-functionalized aniline derivatives in a 100% atom-economical fashion (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

Selective Acid-Catalyzed Hydroarylation of Nonactivated Alkenes with Aniline Assisted by Hexafluoroisopropanol

Peng¹,

Humblot

Wischert³

et al. 2021

J. Org. Chem.

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The catalytic hydroarylation of nonactivated alkenes with aniline is a reaction of high interest, aiming at providing C-functionalized aniline derivatives that are important precursors for the fabrication of polyurethanes. However, this reaction remains a longstanding goal of catalysis, as it requires one to simultaneously address two important goals: (1) the very low reactivity of nonactivated alkenes and (2) control of the hydroarylation/hydroamination selectivity. As a result, the hydroarylation of aniline is mostly restricted to activated alkenes (i.e., featuring ring strain, conjugation, or activation with electron-donating or -withdrawing groups). Here we show that the combination of bismuth triflate and hexafluoroisopropanol (HFIP) leads to the formation of highly active catalytic species capable of promoting the hydroarylation of various nonactivated alkenes, such as 1-octene, 1-heptene, and 1-undecene, among others, with aniline with high selectivity (71–92%). Through a combined experimental and computational investigation, we propose a reaction pathway where HFIP stabilizes the rate-determining transition state through a H-bond interaction with the triflate anion, thus assisting the acid catalyst in the hydroarylation of nonactivated alkenes. From a practical point of view, this work opens a catalytic access to C-functionalized aniline derivatives from two cheap and abundant feedstocks in a 100% atom-economical fashion.

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Scandium-Catalyzed para-Selective Alkylation of Aromatic Amines with Alkenes

Cited by 36 publications

References 47 publications

Aldehyde as a Traceless Directing Group for Regioselective C–H Alkylation Catalyzed by Rhodium(III) in Air

Aldehyde as a Traceless Directing Group for Regioselective C–H Alkylation Catalyzed by Rhodium(III) in Air

On the application of 3d metals for C–H activation toward bioactive compounds: The key step for the synthesis of silver bullets

Selective Acid-Catalyzed Hydroarylation of Nonactivated Alkenes with Aniline Assisted by Hexafluoroisopropanol

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