Nickel Catalysis Enables Access to Thiazolidines from Thioureas via Oxidative Double Isocyanide Insertion Reactions

Yuan, Wen‐Kui; Liu, Yan Fang; Lan, Zhenggang; Wen, Li‐Rong; Li, Ming

doi:10.1021/acs.orglett.8b03098

“…Recently, Li and co‐workers reported the first base metal catalyzed aerobic double isocyanide insertion (Scheme ) to access triiminothiazoles . The authors proposed that molecular oxygen from air facilitates the oxidation of Ni 0 to Ni II , hereby closing the catalytic cycle.…”

Section: Insertions Of Isocyanides Into Heteroatom–metal Bondsmentioning

confidence: 99%

Base Metal Catalyzed Isocyanide Insertions

Collet

¹

,

Roose

²

,

Ruijter

³

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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“…Recently,Liand co-workers reported the first base metal catalyzed aerobic double isocyanideinsertion (Scheme 36) to access triiminothiazoles. [67] Theauthors proposed that molecular oxygen from air facilitates the oxidation of Ni 0 to Ni II , hereby closing the catalytic cycle.T he Ni II -catalyzed reaction tolerates electronically diverse aliphatic and aromatic iso-cyanides.S tarting from non-symmetrical substituted thioureas (138), mixtures of regioisomeric iminothiazoles (139 a/ 139 b,1:1 to 9:1) were obtained in reasonable to good yields.…”

Section: Angewandte Chemiementioning

confidence: 99%

Base Metal Catalyzed Isocyanide Insertions

Collet

¹

,

Roose

²

,

Ruijter

³

et al. 2019

View full text Add to dashboard Cite

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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“…For almost 20 years they have been used as catalysts in organic synthesis, especially in stereoselective reactions [12][13][14]. They also serve as valuable starting materials for the synthesis of heterocycles [15][16][17], and are used as ligands in coordination chemistry (particularly when additional donors are present in their molecules) [18][19][20][21][22], as well as in the field of anion binding and recognition [2,23].…”

Section: Introductionmentioning

confidence: 99%

Chiral Thioureas—Preparation and Significance in Asymmetric Synthesis and Medicinal Chemistry

Steppeler

¹

,

Iwan

²

,

Wojaczyńska

³

et al. 2020

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For almost 20 years, thioureas have been experiencing a renaissance of interest with the emerged development of asymmetric organocatalysts. Due to their relatively high acidity and strong hydrogen bond donor capability, they differ significantly from ureas and offer, appropriately modified, great potential as organocatalysts, chelators, drug candidates, etc. The review focuses on the family of chiral thioureas, presenting an overview of the current state of knowledge on their synthesis and selected applications in stereoselective synthesis and drug development.

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Nickel Catalysis Enables Access to Thiazolidines from Thioureas via Oxidative Double Isocyanide Insertion Reactions

Cited by 32 publications

References 46 publications

Base Metal Catalyzed Isocyanide Insertions

Base Metal Catalyzed Isocyanide Insertions

Base Metal Catalyzed Isocyanide Insertions

Chiral Thioureas—Preparation and Significance in Asymmetric Synthesis and Medicinal Chemistry

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