Mechanism of the Generation of Ketenimine−M(CO)<i><sub>n</sub></i> Complexes (M = Cr, W, Fe) from Fischer Carbenes and Isocyanides

Fernández, Israel; Cossío, Fernando P.; Sierra, Miguel Á.

doi:10.1021/om0701524

Cited by 47 publications

(19 citation statements)

References 50 publications

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“…As shown in Scheme 60, the reaction of Fisher carbene 171 with isocyanide has been developed for the synthesis of ketenes 172. 35 This transformation was mechanistically similar to 1,2-insertion of triple N-C bond of isocyanide into the double MQC bond of carbene.…”

Section: Isocyanide Insertion Into Metal Carbene Compoundsmentioning

confidence: 91%

Recent advances in isocyanide insertion chemistry

2013

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As valuable C1 building blocks, isocyanides represent an important class of reactive species and synthons. During the past decades, exhaustive efforts have been devoted to the discovery of highly efficient reactions involving isocyanide on the basis of the development of the Passerini and Ugi reactions. Several types of reactions involving isocyanides have been reported, such as nucleophilic attack, electrophilic addition, imidoylation reactions, and oxidation etc. In this review, recent progress in isocyanide insertion chemistry is presented. Among all isocyanide insertions, two catalytic systems have been developed, that is, Lewis (Brønsted) acid-catalyzed isocyanide insertions and transition-metal-enabled isocyanide insertions, respectively. This review is hence written in the sequence of Lewis (Brønsted) acid-catalyzed isocyanide insertion and transitional metal-enabled isocyanide insertion, where isocyanide insertion into heteroatom-hydrogen bonds, carbon-halogen bonds, carbon-hydrogen bonds, and metal carbenes are summarized.

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Section: Isocyanide Insertion Into Metal Carbene Compoundsmentioning

confidence: 91%

Recent advances in isocyanide insertion chemistry

2013

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“…Theg eneral mechanism of the insertion of isocyanides via carbene transfer into the TM= Cb ond of Fischer carbenes 147 was extensively investigated in silico by Sierra and co-workers. [69] They showed that am etallacyclopropanimine intermediate 150 is more likely than the previously considered zwitterionic species 149 (Scheme 38). 1,2-Metallotropic rearrangement of 150 then affords N-metalated ketenimine 148.…”

Section: Insertion Of Isocyanides Into Metal Carbene Complexesmentioning

confidence: 98%

Base Metal Catalyzed Isocyanide Insertions

et al. 2019

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Isocyanides are diverse C1 building blocks considering their potential to react with nucleophiles, electrophiles, and radicals. Therefore, perhaps not surprisingly, isocyanides are highly valuable as inputs for multicomponent reactions (MCRs) and other one‐pot cascade processes. In the field of organometallic chemistry, isocyanides typically serve as ligands for transition metals. The coordination of isocyanides to metal centers alters the electronic distribution of the isocyano moiety, and reaction pathways can therefore be accessed that are not possible in the absence of the metal. The tunable reactivity of the isocyanide functional group by transition metals has evolved into numerous useful applications. Especially palladium‐catalyzed isocyanide insertion processes have emerged as powerful reactions in the past decade. However, reports on the use of earth‐abundant and cheap base metals in these types of transformations are scarce and have received far less attention. In this Minireview, we focus on these emerging base metal catalyzed reactions and highlight their potential in synthetic organic chemistry. Although mechanistic studies are still scarce, we discuss distinct proposed catalytic cycles and categorize the literature according to 1) the (hetero)atom bound to and 2) the type of bonding with the transition metal in which the (formal) insertion occurs.

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“…In particular, the reactions of isocyanides with metal carbene complexes are known to form ketenimine complexes, which, in turn, are valuable intermediates and powerful synthetic tools [76]. The mechanism of the reaction of Fischer-type carbenes with methylisocyanide was studied theoretically by DFT method [77,78]. The reaction is believed to proceed via metallacyclopropanimine species which are generated by nucleophilic attack of the isocyanide carbon atom on the electrophilic carbene carbon (Scheme 6).…”

Section: Addition Of Isocyanides To Coordinated Ligandsmentioning

confidence: 99%

Bond Forming Reactions Involving Isocyanides at Diiron Complexes

et al. 2019

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The versatility of isocyanides (CNR) in organic chemistry has been tremendously enhanced by continuous advancement in transition metal catalysis. On the other hand, the urgent need for new and more sustainable synthetic strategies based on abundant and environmental-friendly metals are shifting the focus towards iron-assisted or iron-catalyzed reactions. Diiron complexes, taking advantage of peculiar activation modes and reaction profiles associated with multisite coordination, have the potential to compensate the lower activity of Fe compared to other transition metals, in order to activate CNR ligands. A number of reactions reported in the literature shows that diiron organometallic complexes can effectively assist and promote most of the “classic” isocyanide transformations, including CNR conversion into carbyne and carbene ligands, CNR insertion, and coupling reactions with other active molecular fragments in a cascade sequence. The aim is to evidence the potential offered by diiron coordination of isocyanides for the development of new and more sustainable synthetic strategies for the construction of complex molecular architectures.

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Mechanism of the Generation of Ketenimine−M(CO)_n Complexes (M = Cr, W, Fe) from Fischer Carbenes and Isocyanides

Cited by 47 publications

References 50 publications

Recent advances in isocyanide insertion chemistry

Recent advances in isocyanide insertion chemistry

Base Metal Catalyzed Isocyanide Insertions

Bond Forming Reactions Involving Isocyanides at Diiron Complexes

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Mechanism of the Generation of Ketenimine−M(CO)n Complexes (M = Cr, W, Fe) from Fischer Carbenes and Isocyanides

Cited by 47 publications

References 50 publications

Recent advances in isocyanide insertion chemistry

Recent advances in isocyanide insertion chemistry

Base Metal Catalyzed Isocyanide Insertions

Bond Forming Reactions Involving Isocyanides at Diiron Complexes

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Product

Resources

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Mechanism of the Generation of Ketenimine−M(CO)_n Complexes (M = Cr, W, Fe) from Fischer Carbenes and Isocyanides