Catalyst-free electrochemical decarboxylative cross-coupling of N-hydroxyphthalimide esters and N-heteroarenes towards C(sp3)–C(sp2) bond formation

Liu, Yichang; Xue, Liwei; Shi, Biyin; Bu, Faxiang; Wang, Dan; Lu, Lijun; Shi, Renyi; Lei, Aiwen

doi:10.1039/c9cc08528a

Cited by 63 publications

(31 citation statements)

References 41 publications

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“…In the past decades, electrochemical reaction protocols have shown the potential to be versatile and sustainable methods for the synthesis of organic compounds, and have attracted considerable attention [8] . Under electrochemical oxidative conditions, substrates could be oxidized through single electron transfer to construct various new bonds [9–15] . In particular, electrochemical C−X formation is a useful way to construct electrophiles, which can be utilized for further synthetic manipulations [15a,16] .…”

Section: Methodsmentioning

confidence: 99%

Electrochemical Oxidative Functionalization of Arylalkynes: Access to α,α‐Dibromo Aryl Ketones

et al. 2020

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A general and effective protocol to synthesize α,α‐dibromo aryl ketones has been developed via an electrochemical oxidative method. The reaction proceeds smoothly at room temperature in an undivided cell without the addition of external oxidants. In the reaction process, LiBr acts as both bromine source and supporting electrolyte. This electrooxidation strategy has good substrate applicability and functional group compatibility. Moreover, the reaction could be scaled up efficiently in a continuous flow cell. The target product could undergo further functionalization for the synthesis of some useful heterocyclic compounds.

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Section: Methodsmentioning

confidence: 99%

Electrochemical Oxidative Functionalization of Arylalkynes: Access to α,α‐Dibromo Aryl Ketones

et al. 2020

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“…Redox‐active N ‐hydroxyphthalimide (NHP) esters from readily accessible alkyl carboxylic acids have been recognized as versatile alkyl radical precursors for applications in cross‐coupling reactions [21] . In 2019, Lei, Shi, and co‐workers reported a catalyst‐free electrochemical decarboxylative coupling of NHP esters with N ‐heteroarenes (Figure 9A) [22] . A wide range of primary, secondary, tertiary aliphatic carboxylic acids derived NHP esters as well as one example of pyridinium salt‐from the corresponding aliphatic amine, could be employed as alkyl radical precursors (Figure 9B).…”

Section: Sequential Paired Electrolysismentioning

confidence: 99%

Reaching the Full Potential of Electroorganic Synthesis by Paired Electrolysis

Zhang

Hong

et al. 2021

The Chemical Record

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Electroorganic synthesis has recently become a rapidly blossoming research area within the organic synthesis community. It should be noted that electrochemical reaction is always a balanced reaction system with two half‐cell reactions‐oxidation and reduction. Most electrochemical strategies, however, typically focus on one of the two sides for the desired transformations. Paired electrolysis has two desirable half reactions running simultaneously, thus maximizing the overall margin of atom and energy economy. Meanwhile, the spatial separation between oxidation and reduction is the essential feature of electrochemistry, offering unique opportunities for the development of redox‐neutral reactions that would otherwise be challenging to accomplish in a conventional reaction flask setting. This review discusses the most recent illustrative examples of paired electrolysis with special emphasis on sequential and convergent processes.

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“…Shi, Lei and coworkers developed a catalyst-free C(sp 2 )À C(sp 3 ) coupling of N-heteroarenes 1 and aliphatic NHPI esters 5 under electrochemical conditions to achieve Minisci-type alkylations of quinolines and isoquinolines furnishing corresponding products 20 in moderate to good yields (Scheme 12). [50] It was proposed that initially, NHPI ester 5 gets reduced by accepting one electron at the cathode to form a radical anion A, which immediately undergoes cleavage to generate an alkyl radical B through the elimination of CO 2 and phthalimide anion. Subsequent to its generation alkyl radical B undergoes addition on the protonated heterocycle 1 leading to a radical cation species C. Finally, through the loss of an electron at anode, C delivers D, which upon deprotonation furnishes the final product 20.…”

Section: Heteroarenes Containing One Heteroatommentioning

confidence: 99%

Late‐Stage Alkylation of Heterocycles Using N‐(Acyloxy)phthalimides

Parida

Hota

Kumar

et al. 2021

Chemistry An Asian Journal

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Synthetic methods enabling late-stage modification of heterocycles hold tremendous importance in the pharmaceutical and agrochemical industry and drug discovery. Accordingly, efficient, functional group tolerant and selective late-stage alkylation of valuable molecular entities is of enormous significance and well-acknowledged in medicinal chemistry. Radical alkylation of heteroarenes employing carboxylic acids as the alkyl radical precursor represents one of the most direct ways of CÀ H functionalizations of heterocycles. Recently, the field has undergone a revolutionary development especially with regard to the generation of alkyl radicals under much milder conditions. In this regard N-(acyloxy)phthalimides (NHPI esters) have emerged as a suitable precursor of a diverse set of alkyl radicals allowing formal CÀ H alkylation of not only N-heteroarenes but a diverse set of non-aromatic heterocycles under visible light photocatalysis or electrochemical conditions. This review delineates all these discoveries and provides readers a comprehensive overview of this rapidly expanding field.

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Catalyst-free electrochemical decarboxylative cross-coupling of N-hydroxyphthalimide esters and N-heteroarenes towards C(sp³)–C(sp²) bond formation

Abstract: We formed C(sp3)–C(sp2) bonds under electrochemical conditions by using NHP esters and N-heteroarenes without any catalysts. Our approach could be a complement to the Kolbe reaction and a promising strategy for finding more new reactions.

Cited by 63 publications

References 41 publications

Electrochemical Oxidative Functionalization of Arylalkynes: Access to α,α‐Dibromo Aryl Ketones

Electrochemical Oxidative Functionalization of Arylalkynes: Access to α,α‐Dibromo Aryl Ketones

Reaching the Full Potential of Electroorganic Synthesis by Paired Electrolysis

Late‐Stage Alkylation of Heterocycles Using N‐(Acyloxy)phthalimides

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