Base Metal Catalyzed Isocyanide Insertions

Research output: Contribution to JournalReview articleAcademicpeer-review

Abstract

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.

Original languageEnglish
Number of pages20
JournalAngewandte Chemie - International Edition
DOIs
Publication statusE-pub ahead of print - 9 Jul 2019

Fingerprint

Cyanides
Metals
Transition metals
Nucleophiles
Organometallics
Functional groups
Palladium
Earth (planet)
Ligands
Atoms

Keywords

  • base metal catalysis
  • C building blocks
  • imidoylation
  • isocyanides
  • synthetic methods

Cite this

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title = "Base Metal Catalyzed Isocyanide Insertions",
abstract = "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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Base Metal Catalyzed Isocyanide Insertions. / Collet, Jurriën W.; Roose, Thomas R.; Ruijter, Eelco; Maes, Bert U.W.; Orru, Romano V.A.

In: Angewandte Chemie - International Edition, 09.07.2019.

Research output: Contribution to JournalReview articleAcademicpeer-review

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T1 - Base Metal Catalyzed Isocyanide Insertions

AU - Collet, Jurriën W.

AU - Roose, Thomas R.

AU - Ruijter, Eelco

AU - Maes, Bert U.W.

AU - Orru, Romano V.A.

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AB - 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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