Decarboxylative Alkynylation and Carbonylative Alkynylation of Carboxylic Acids Enabled by Visible‐Light Photoredox Catalysis

Zhou, Quan‐Quan; Guo, Wei; Ding, Wei; Xiong, Wu; Chen, Xi; Lu, Liang‐Qiu; Xiao, Wen‐Jing

doi:10.1002/anie.201504559

Cited by 288 publications

(102 citation statements)

References 65 publications

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“…First, it has been reported that this process is not high yielding. [14a, 14c, 18] Second, our studies have shown that the ligand on nickel is essential to bond formation but not consumption of the NHP ester (Table 1, entry 12). [13a] Third, the major challenge during reaction optimization was too-rapid consumption of the bromoalkyne and subsequent diyne formation, a process that requires an alkynylnickel intermediate (Table 1 and Scheme 3d).…”

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confidence: 98%

“…For example, the oxidative decarboxylation of aliphatic acids to form alkyl radicals with subsequent capture by alkynyl electrophiles. [14] Concurrent with these studies, Fu reported on the coupling of terminal alkynes with α-amino NHP esters [15] and Baran reported on the coupling of N -hydroxytetrachlorophthalimide (TCNHPI) esters with alkynylzinc or magnesium reagents. [16] Our proposed approach would avoid the need for organometallic reagents and the more expensive TCNHPI [17] without being limited to α-amino acid derivatives.…”

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confidence: 99%

“…[15] Although this approach would use alkyne electrophiles, bromoalkynes [7] are more easily prepared than ethynylbenziodoxolones [18] or alkynyl sulfones. [14a–c] …”

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confidence: 99%

“…Three potential mechanisms were proposed: 1) in-situ formation of an alkynyl manganese reagent and subsequent nickel-catalyzed cross-coupling, [16] 2) nickel-catalyzed radical generation [13b, 23],[13a] and outer-sphere addition of the free radical to the bromoalkyne; [14a–c] 3) sequential reaction of two electrophiles with the nickel catalyst and bond-formation at nickel. [24] At this time, we can rule out the first two mechanistic possibilities ( vide infra ).…”

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confidence: 99%

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Reductive Decarboxylative Alkynylation of N‐Hydroxyphthalimide Esters with Bromoalkynes

2017

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A new method for the synthesis of terminal and internal alkynes from the nickel-catalyzed decarboxylative coupling of N-hydroxyphthalimide esters (NHP esters) and bromoalkynes is presented. This reductive cross-electrophile coupling is the first to use a C(sp)-X electrophile, and appears to proceed via an alkynylnickel intermediate. The internal alkyne products are obtained in 41–95% yield without the need for a photocatalyst, light, or strong oxidant. The reaction displays a broad scope of carboxylic acid and alkyne coupling partners and can tolerate an array of functional groups including a carbamate N-H, halogen, nitrile, olefin, ketone, and ester. Mechanistic studies suggest that this process does not involve an alkynylmanganese reagent and involves nickel-mediated bond formation.

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confidence: 98%

mentioning

confidence: 99%

“…[15] Although this approach would use alkyne electrophiles, bromoalkynes [7] are more easily prepared than ethynylbenziodoxolones [18] or alkynyl sulfones. [14a–c] …”

mentioning

confidence: 99%

mentioning

confidence: 99%

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Reductive Decarboxylative Alkynylation of N‐Hydroxyphthalimide Esters with Bromoalkynes

2017

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“…As a testimony of the current intensive research in photoredox catalysis, Xiao and co-workers also published a very similar approach simultaneously with our work. 57 Further applications combining photoredox catalysis and benziodoxole reagents can be expected in the future. 12, B).…”

Section: New Partners For Ebx Reagentsmentioning

confidence: 99%

Benziodoxol(on)e Reagents as Tools in Organic Synthesis: The Background behind the Discovery at the Laboratory of Catalysis and Organic Synthesis

Waser

2016

Synlett

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In this review, a personal account of our work in the field of hypervalent iodine reagents is presented. Pioneering experiments, which led to the discovery of the exceptional reactivity of EthynylBenziodoXol(on)e (EBX) reagents as electrophilic alkyne synthons is first discussed, including the alkynylation of ketoesters, olefins and heterocycles. Our further work involving EBX reagents in domino reactions and the alkynylation of thiols, as well as the use of benziodoxole reagents for azidation reactions is then described. Finally, the most recent results involving radicals and carbenes as reaction partners for EBX reagents and their first use in chemical biology are presented. The purpose of this review is not to give an extensive overview of our results, but to show the "true story" beyond the discovery by presenting the most important pioneering experiments. Failed attempts and near misses are also shortly discussed.

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Alkynylations and Vinylations

Hari

Nicolai

Waser

2018

Patai's Chemistry of Functional Groups

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Alkynes and alkenes are important building blocks in synthetic organic chemistry and related domains. Therefore, unceasing efforts have been invested to develop new methods to introduce these valuable functional groups. Traditionally, most alkynylation and alkenylation reactions have relied on the use of olefins and acetylenes as nucleophilic reacting species, limiting the accessible structural diversity. The discovery of the unique properties of hypervalent iodine has more recently significantly broadened the scope of electrophilic ethynylation and vinylation reactions. Alkynyl and alkenyl iodonium salts were first recognized as powerful reagents to install electrophilic acetylenes and olefins onto nucleophilic substrates under mild conditions. Their low stability has however narrowed the area of their applications. Since 2009, more stable cyclic benziodoxol(on)e reagents have shown their superiority as effective electrophilic alkynylating and alkenylating reagents in numerous metal-free and metal-catalyzed olefination and ethynylation reactions of carbon centered nucleophiles, radicals, and heteroatom nucleophiles. In this chapter, an overview of the progress in the field is presented, including a short summary of pioneering works, followed by a more in-depth description of recent results.

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Decarboxylative Alkynylation and Carbonylative Alkynylation of Carboxylic Acids Enabled by Visible‐Light Photoredox Catalysis

Cited by 288 publications

References 65 publications

Reductive Decarboxylative Alkynylation of N‐Hydroxyphthalimide Esters with Bromoalkynes

Reductive Decarboxylative Alkynylation of N‐Hydroxyphthalimide Esters with Bromoalkynes

Benziodoxol(on)e Reagents as Tools in Organic Synthesis: The Background behind the Discovery at the Laboratory of Catalysis and Organic Synthesis

Alkynylations and Vinylations

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