Metal-Catalyzed Cross-Coupling of Terminal Alkynes with Different Carbene Precursors

Che, Jiuwei; Xing, Dong; Hu, Wenhao

doi:10.2174/1385272819666151008014517

Cited by 21 publications

(8 citation statements)

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“…The new organometallic species generated from migratory insertion may undergo various transformations, such as β-hydride elimination, protonation, transmetalation/reductive elimination, etc. The carbene-based couplings have proven to be general: the complexes of various transition-metals, including Pd, Cu, Rh, Ni, Co, and Ir, are effective catalysts; the scope of the reaction has also been extended to substrates other than diazo compounds; 83,84 and various cascade processes can be devised based on the carbene migratory insertion process (Scheme 17). This review will cover the transition-metal-catalyzed crosscouplings with carbene precursors involving carbene migratory insertion reported in the literature up to April 2017, while those stoichiometric carbene coupling reactions, 59−72,86−95 carbenerelated reactions not involving a migratory insertion process, 43−47 and carbene polymerization 97 are not in the scope of this review.…”

Section: General Principle Of Coupling With Carbene Precursorsmentioning

confidence: 99%

“…Further, Green and co-workers carried out kinetic studies of tungsten carbene migratory insertion to the metal-hydride bond . Since then, more stoichiometric studies on migratory insertion of metal carbene complex to metal-hydride or metal–carbon bonds have appeared in the literature, ,− which provided understanding for the recently developed transition-metal-catalyzed cross-coupling process involving carbene process. − …”

Section: Introductionmentioning

confidence: 99%

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Transition-Metal-Catalyzed Cross-Couplings through Carbene Migratory Insertion

2017

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Transition-metal-catalyzed cross-coupling reactions have been well-established as indispensable tools in modern organic synthesis. One of the major research goals in cross-coupling area is expanding the scope of the coupling partners. In the past decade, diazo compounds (or their precursors N-tosylhydrazones) have emerged as nucleophilic cross-coupling partners in C-C single bond or C═C double bond formations in transition-metal-catalyzed reactions. This type of coupling reaction involves the following general steps. First, the organometallic species is generated by various processes, including oxidative addition, transmetalation, cyclization, C-C bond cleavage, and C-H bond activation. Subsequently, the organometallic species reacts with the diazo substrate to generate metal carbene intermediate, which undergoes rapid migratory insertion to form a C-C bond. The new organometallic species generated from migratory insertion may undergo various transformations. This type of carbene-based coupling has proven to be general: various transition metals including Pd, Cu, Rh, Ni, Co, and Ir are effective catalysts; the scope of the reaction has also been extended to substrates other than diazo compounds; and various cascade processes have also been devised based on the carbene migratory insertion. This review will summarize the achievements made in this field since 2001.

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Section: General Principle Of Coupling With Carbene Precursorsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Transition-Metal-Catalyzed Cross-Couplings through Carbene Migratory Insertion

2017

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“…Copper-catalyzed cross-coupling reaction of a copper carbene intermediate with terminal alkynes was one of the most powerful protocols for the construction of C–C bonds [ 87 ]. However, in early works, a mixture of alkynoates and allenoates was generated in combined moderate yields under harsh reaction conditions [ 88 ].…”

Section: Cross-coupling Reaction Of Copper Carbene Intermediate With ...mentioning

confidence: 99%

Recent Advances in Catalytic Alkyne Transformation via Copper Carbene Intermediates

Dong

Liu

2022

Molecules

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As one of the abundant and inexpensive metals on the earth, copper has demonstrated broad applications in synthetic chemistry and catalysis. Among these copper-catalyzed advances, copper carbenes are versatile and reactive intermediates that can mediate a variety of transformations, which have attracted much attention in the past decades. The present review summarizes two different reaction models that take place between a copper carbene intermediate and alkyne species, including the cross-coupling reaction of copper carbene intermediate with terminal alkyne, and the addition of copper carbene intermediate onto the C–C triple bond. This article will cover the profile from 2010 to 2021 by placing emphasis on the detailed catalytic models and highlighting the synthetic applications offered by these practical and mild methods.

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“…All group 11 metals are involved in catalytic reactions that may form intermediate reactive metal carbenes in one of the steps of the process . For example, the mechanisms of alkene cyclopropanation, carbene insertion reactions into C–H bonds of alkanes, coupling reactions of diazo compounds, and the Wolff rearrangement involve the formation of elusive metal–carbene species from the diazo derivatives used as reagents and this has been supported by DFT calculations . Cycloheptatrienes as carbene precursors by a retro-Buchner reaction have been used in a gold-catalyzed cyclopropanation reaction with the likely participation of a gold carbene species .…”

Section: Introductionmentioning

confidence: 96%

Transmetalation of Acyclic Tungsten Carbenes to Coinage Metals: Distinct Behavior of Silver toward Carbene Transfer and Hydrolysis

et al. 2020

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The transmetalation of acyclic monoamino and alkoxo carbenes from tungsten to group 11 metals has been studied for all three metals by analyzing the new metal carbenes formed and also their decomposition products in solution. The ease of transmetalation follows the trend: Au > Cu > Ag and the gold carbenes can be isolated, a copper carbene could be detected but we found no experimental evidence of the formation of any silver carbene. The electrophilic character of copper and gold carbenes is supported by the identity of the products formed upon hydrolysis of the carbenes involved. Silver shows a distinct behavior and the presence of Ag + ions in an acetonitrile solution of a tungsten aminocarbene leads to the formal protonation of the carbene fragment to give an iminium salt. This outcome, a seemingly nucleophillic behavior, is unexpected for group 11 carbenes but DFT calculations show that the protonation of a putative cationic silver carbene is energetically accessible.

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Metal-Catalyzed Cross-Coupling of Terminal Alkynes with Different Carbene Precursors

Cited by 21 publications

References 0 publications

Transition-Metal-Catalyzed Cross-Couplings through Carbene Migratory Insertion

Transition-Metal-Catalyzed Cross-Couplings through Carbene Migratory Insertion

Recent Advances in Catalytic Alkyne Transformation via Copper Carbene Intermediates

Transmetalation of Acyclic Tungsten Carbenes to Coinage Metals: Distinct Behavior of Silver toward Carbene Transfer and Hydrolysis

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