Electrochemical selenium–π–acid promoted hydration of alkynyl phosphonates

Li, Bo; Zhou, Yunhao; Sun, Yanan; Xiong, Feng; Gu, Linghui; Ma, Wenbo; Mei, Ruhuai

doi:10.1039/d2cc01901a

Cited by 18 publications

(12 citation statements)

References 65 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In 2022, Mei proposed an elegant regioselective β-hydration of alkynyl phosphonates 73 via electrochemical oxidative organoselenium catalysis (Scheme 42). 84 The authors showed that the combination of organic electrosynthesis and selenium catalysis (PhSeSePh) promoted an electrophilic PhSe + cationic species. A plausible mechanism involving the assistance of the phosphonate group was proposed by the authors and was supported by H/D exchange, the 18 O label, and radical scavenger experiments.…”

Section: β-Hydration Of Alkynesmentioning

confidence: 99%

Hydration of Unsymmetrical Internal Alkynes: Factors Governing the Regioselectivity

et al. 2023

View full text Add to dashboard Cite

Water addition on an unsymmetrical internal alkyne has significance in organic chemistry and has stimulated challenging approaches to access a highly regioselective process. Hydration or formal hydration is presented according to the type of internal alkyne. Methods for electron-rich and -poor diarylalkynes followed by those adapted to arylalkylalkynes are presented. Regioselective hydration reactions of unsymmetrical propargylic and homopropargylic derivatives are then discussed, followed by regioselective aspects of the hydration of internal alkynes directed by carbonyl groups. The following section examines the hydration alkynes linked to CF 3 , esters, ketones, and heteroatoms as haloalkynes, alkynylphosphonates, ynamides, and others. At the end of this section, we report some recent examples of hydration reactions where the alkyne triple bond is connected to an electron-withdrawing group as an ester or a ketone. Reactions are presented, discussed, and illustrated in each of these items through various representative examples. The mechanistic hypotheses explaining the origin of the regioselectivity in the hydration reactions are discussed. This review of recent advances in the regioselective hydration of internal unsymmetrical alkynes (from 2007 until the present) aims to update the current body of knowledge and aid researchers working in this field.

show abstract

Section: β-Hydration Of Alkynesmentioning

confidence: 99%

Hydration of Unsymmetrical Internal Alkynes: Factors Governing the Regioselectivity

et al. 2023

View full text Add to dashboard Cite

show abstract

“…The authors have cited additional references within the Supporting Information [14,24,28,33,37,40–62] …”

Section: Figurementioning

confidence: 99%

Efficient C(sp³)−H Carbonylation of Light and Heavy Hydrocarbons with Carbon Monoxide via Hydrogen Atom Transfer Photocatalysis in Flow**

et al. 2023

View full text Add to dashboard Cite

Despite their abundance in organic molecules, considerable limitations still exist in synthetic methods that target the direct C−H functionalization at sp3‐hybridized carbon atoms. This is even more the case for light alkanes, which bear some of the strongest C−H bonds known in Nature, requiring extreme activation conditions that are not tolerant to most organic molecules. To bypass these issues, synthetic chemists rely on prefunctionalized alkyl halides or organometallic coupling partners. However, new synthetic methods that target regioselectively C−H bonds in a variety of different organic scaffolds would be of great added value, not only for the late‐stage functionalization of biologically active molecules but also for the catalytic upgrading of cheap and abundant hydrocarbon feedstocks. Here, we describe a general, mild and scalable protocol which enables the direct C(sp3)−H carbonylation of saturated hydrocarbons, including natural products and light alkanes, using photocatalytic hydrogen atom transfer (HAT) and gaseous carbon monoxide (CO). Flow technology was deemed crucial to enable high gas‐liquid mass transfer rates and fast reaction kinetics, needed to outpace deleterious reaction pathways, but also to leverage a scalable and safe process.

show abstract

“…In 2022, Mei’s group developed an efficient phosphonate-assisted hydration of internal alkynes 9 via electro-catalysis with a PhSeSePh mediator (Scheme 3 ). 9 Employing room temperature conditions, utilizing RVC as the anode, platinum plate as the cathode, CH 3 CN as the solvent, Et 4 NBF 4 as the electrolyte, and a constant current of 10 mA, the reaction, catalyzed by 0.5 equivalent of PhSeSePh, proceeded between acetylenes and phosphonic acid groups to furnish a series of (heterogeneous) aryl and alkyl ketone compounds 10 . This protocol showcases remarkable chemo-/regioselectivity and scalability with internal alkynes harboring diverse functional groups, enabling facile access to a broad spectrum of (hetero) aryl and alkyl ketones with high efficiency.…”

Section: Electrochemical Selenium-catalyzed Reactionsmentioning

confidence: 99%

Recent Advances in Electrochemically Mediated Reactions of Diselenides

Mo,

Pan,

Zhan

et al. 2023

SynOpen

View full text Add to dashboard Cite

Organoselenium compounds are crucial molecules extensively utilized in diverse fields such as medicine, agriculture, catalysis, and organic materials. The incorporation of selenium atoms into organic molecules holds significant importance in synthetic chemistry. Organic electrochemical synthesis, a green, mild, and efficient strategy, has displayed remarkable potential for organoselenium chemistry synthesis. Consequently, there has been substantial interest in recent years in researching electrochemically mediated synthesis of organoselenium compounds. This review provides an overview of the progress made in electrochemically mediated organic selenium reactions over the last decade, including electrochemical mediated selenium catalysis, electrochemical oxidation of diselenides coupling, and electrochemical oxidation tandem selenocyclization. The scope, limitations, and mechanisms of those reactions were emphasized.

show abstract

Electrochemical selenium–π–acid promoted hydration of alkynyl phosphonates

Abstract: An unprecedented electrochemical selenium-π-acid promoted hydration of internal alkyne assisted via phosphonates was described. Thus, valuable (hetro)aryl and alkyl ketones could be accessed under mild, metal- and external oxidant-free conditions....

Cited by 18 publications

References 65 publications

Hydration of Unsymmetrical Internal Alkynes: Factors Governing the Regioselectivity

Hydration of Unsymmetrical Internal Alkynes: Factors Governing the Regioselectivity

Efficient C(sp³)−H Carbonylation of Light and Heavy Hydrocarbons with Carbon Monoxide via Hydrogen Atom Transfer Photocatalysis in Flow**

Recent Advances in Electrochemically Mediated Reactions of Diselenides

Contact Info

Product

Resources

About

Electrochemical selenium–π–acid promoted hydration of alkynyl phosphonates

Abstract: An unprecedented electrochemical selenium-π-acid promoted hydration of internal alkyne assisted via phosphonates was described. Thus, valuable (hetro)aryl and alkyl ketones could be accessed under mild, metal- and external oxidant-free conditions....

Cited by 18 publications

References 65 publications

Hydration of Unsymmetrical Internal Alkynes: Factors Governing the Regioselectivity

Hydration of Unsymmetrical Internal Alkynes: Factors Governing the Regioselectivity

Efficient C(sp3)−H Carbonylation of Light and Heavy Hydrocarbons with Carbon Monoxide via Hydrogen Atom Transfer Photocatalysis in Flow**

Recent Advances in Electrochemically Mediated Reactions of Diselenides

Contact Info

Product

Resources

About

Efficient C(sp³)−H Carbonylation of Light and Heavy Hydrocarbons with Carbon Monoxide via Hydrogen Atom Transfer Photocatalysis in Flow**