The Copper‐Catalyzed Decarboxylative Coupling of the sp<sup>3</sup>‐Hybridized Carbon Atoms of α‐Amino Acids

Bi, Hai‐Peng; Zhao, Liang; Liang, Yong‐Min; Li, Chao‐Jun

doi:10.1002/anie.200805122

Cited by 295 publications

(79 citation statements)

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“…The combined organic layers were dried over MgSO4, filtered and the solvent was evaporated under reduced pressure. The resulting solid was triturated in hexane (10 mL 7,132.5,132.4,119.7,117.6,117.6,44.9,18.3,11.1;IR ν 3288 (w), 3088 (m), 2949 (m), 2894 [6] Y. LI, J. Brand, J. Waser, Angew.…”

Section: Phenyl(triisopropylsilyl)iodonium Triflate (1c)mentioning

confidence: 99%

“…In 2009, Chao-Jun Li and co-workers reported the decarboxylative alkynylation of amino acids using a copper catalyst and di-tert-butyl peroxide as stoichiometric oxidant at 110 °C (Scheme 2, A). [6] In 2010, Seidel and co-workers [7] and Chao-Jun Li and coworkers [8] used the condensation of aldehydes or ketones instead of the peroxide oxidant (Scheme 2, B). The copper-catalyzed method was extended to -cyano carboxylic acids by Xu and co-workers in 2013 using alkynyl bromides (Scheme 2, C).…”

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confidence: 99%

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Room‐Temperature Decarboxylative Alkynylation of Carboxylic Acids Using Photoredox Catalysis and EBX Reagents

2015

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Alkynes are used as building blocks in synthetic and medicinal chemistry, chemical biology and materials science. Therefore, efficient methods for their synthesis are the subject of intensive research. Herein, we report the synthesis of alkynes directly from broadly available carboxylic acids at room temperature under visible light irradiation. The combination of an iridium photocatalyst with EthynylBenziodoXolone (EBX) reagents allowed the decarboxylative alkynylation of carboxylic acids in good yields under mild conditions. The method could be applied to the transfer of silyl-, aryl-and alkyl-substituted alkynes. It was especially successful in the case of -amino and -oxo acids derived from the biomass.Alkynes are among the most versatile functional groups in synthetic chemistry, as they are sufficiently stable, yet reactive enough to be easily modified. These properties made them ideally suited for applications not only in organic synthesis, but also in chemical biology and materials science (Scheme 1).[1] All potential applications remain tributary of an efficient synthesis of alkynes. In particular, the metalcatalyzed Sonogashira cross-coupling is now broadly applied to access acetylenes (Scheme 1, A).[2] However, the Sonogashira reaction requires starting materials functionalized with adequate leaving groups, which themselves need to be introduced into the molecules. New approaches are urgently needed to make the synthesis of structurally diverse alkynes more efficient. To meet this challenge, the direct alkynylation of SP 2[3] or SP 3[4] C-H bonds has been intensively investigated in the last decade (Scheme 1, B). Nevertheless, many of these methods still suffer from harsh conditions, limited scope and the need for directing groups or adjacent heteroatoms to control the selectivity in C-H functionalization. Scheme 1. Synthesis and applications of alkynes.As an alternative to classical cross-coupling or C-H functionalization, decarboxylative methods have recently attracted strong interest (Scheme 1, C).[5] Indeed, the required carboxylic acids starting materials are derived from the biomass, and are therefore often even cheaper than the corresponding C-H compounds. Furthermore, the carboxy group allows controlling the site of functionalization and only carbon dioxide is generated as waste. Despite these advantages, examples of decarboxylative alkynylation of aliphatic carboxylic acids are rare (Scheme 2). In 2009, Chao-Jun Li and co-workers reported the decarboxylative alkynylation of amino acids using a copper catalyst and di-tert-butyl peroxide as stoichiometric oxidant at 110 °C (Scheme 2, A). [6] In 2010, Seidel and co-workers [7] and Chao-Jun Li and coworkers [8] used the condensation of aldehydes or ketones instead of the peroxide oxidant (Scheme 2, B). The copper-catalyzed method was extended to -cyano carboxylic acids by Xu and co-workers in 2013 using alkynyl bromides (Scheme 2, C).[9] Finally, in 2012, Chaozhong Li and co-workers reported a different approach based on the oxidative...

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Section: Phenyl(triisopropylsilyl)iodonium Triflate (1c)mentioning

confidence: 99%

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confidence: 99%

Room‐Temperature Decarboxylative Alkynylation of Carboxylic Acids Using Photoredox Catalysis and EBX Reagents

2015

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“…Therefore, using α-amino acids as the nitrogen-containing motifs to construct heterocycles are very attractive synthetic method. Many reactions about the decarboxylative of α-amino acids have been developed in recent years [32][33][34][35][36][37][38][39][40][41][42]. For example, Fu and our group have reported the synthesis of quinazolinones via a decarboxylative coupling of α-amino acids [43,44].…”

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confidence: 99%

Metal-free synthesis of polysubstituted oxazoles via a decarboxylative cyclization from primary α-amino acids

Guo

Zha

et al. 2013

sustain chem process

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Background: The ubiquitous oxazoles have attracted more and more attention in both industrial and academic fields for decades. This interest arises from the fact that a variety of natural and synthetic compounds which contain the oxazole substructure exhibit significant biological activities and antiviral properties. Although various synthetic methodologies for synthesis of oxazols have been reported, the development of milder and more general procedure to access oxazoles is still desirable. Results: In this manuscript, a novel method for synthesis of polysubstituted oxazoles was developed from metalfree decarboxylative cyclization of easily available primary α-amino acids with 2-bromoacetophenones. Conclusions:The method was simple, and this reaction could be carried out smoothly under mild and metal-free conditions. By virtue of this method, various polysubstituted oxazoles were obtained from the primary α-amino acids with moderate yields.

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“…Während die Knüpfung von C(sp)-C(sp 2 )-Bindungen durch die Sonogashira-Reaktion [6] gut entwickelt ist, gibt es nur wenige Methoden für die Kupplung zwischen C(sp 3 )-und C(sp)-Zentren. [7][8][9][10] Diese Reaktionen werden durch konkurrierende b-Hydrideliminierung und eine langsame reduktive Eliminierung erschwert. [7] Die meisten der heute vorliegenden Methoden beruhen auf der Kupplung einer metallorganischen Alkinylverbindung oder eines Alkins mit einem Alkylhalogenid.…”

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“…[10] Stereoselektive Varianten dieser Reaktionen sind selten und wurden bis dato nur für C(sp)-C(sp 3 )-Kreuzkupplungen entwickelt. [8f,g] Vor kurzem konnten wir zeigen, dass sich die Pd-Katalyse zur Durchführung hoch diastereoselektiver C(sp 3 )-C(sp 2 )-Negishi-Kreuzkupplungen zwischen substituierten Cycloalkylreagentien und (Hetero)Arylhalogeniden eignet.…”

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Hoch diastereoselektive C(sp³)‐C(sp)‐Kreuzkupplungen zwischen 1,3‐ und 1,4‐substituierten Cyclohexylzinkreagentien und Bromalkinen

et al. 2011

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The Copper‐Catalyzed Decarboxylative Coupling of the sp³‐Hybridized Carbon Atoms of α‐Amino Acids

Cited by 295 publications

References 62 publications

Room‐Temperature Decarboxylative Alkynylation of Carboxylic Acids Using Photoredox Catalysis and EBX Reagents

Room‐Temperature Decarboxylative Alkynylation of Carboxylic Acids Using Photoredox Catalysis and EBX Reagents

Metal-free synthesis of polysubstituted oxazoles via a decarboxylative cyclization from primary α-amino acids

Hoch diastereoselektive C(sp³)‐C(sp)‐Kreuzkupplungen zwischen 1,3‐ und 1,4‐substituierten Cyclohexylzinkreagentien und Bromalkinen

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The Copper‐Catalyzed Decarboxylative Coupling of the sp3‐Hybridized Carbon Atoms of α‐Amino Acids

Cited by 295 publications

References 62 publications

Room‐Temperature Decarboxylative Alkynylation of Carboxylic Acids Using Photoredox Catalysis and EBX Reagents

Room‐Temperature Decarboxylative Alkynylation of Carboxylic Acids Using Photoredox Catalysis and EBX Reagents

Metal-free synthesis of polysubstituted oxazoles via a decarboxylative cyclization from primary α-amino acids

Hoch diastereoselektive C(sp3)‐C(sp)‐Kreuzkupplungen zwischen 1,3‐ und 1,4‐substituierten Cyclohexylzinkreagentien und Bromalkinen

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The Copper‐Catalyzed Decarboxylative Coupling of the sp³‐Hybridized Carbon Atoms of α‐Amino Acids

Hoch diastereoselektive C(sp³)‐C(sp)‐Kreuzkupplungen zwischen 1,3‐ und 1,4‐substituierten Cyclohexylzinkreagentien und Bromalkinen