Metal carbonyls catalysed reaction of isocyanates with aldehydes

Drapier, J.M.; Hoornaerts, M.T.; Hubert, Aurélia; Teyssié, Ph.

doi:10.1016/0304-5102(81)85066-3

Cited by 12 publications

(6 citation statements)

References 40 publications

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“…28,29,89−91 Isocyanates have also been cross-metathesized by phospholene oxides as well as imido, oxo, and carbonyl TM complexes, yielding carbodiimides and CO 2(g) , [48][49][50]92 though alternative mechanisms have also been proposed for these systems. 93,94 Cross-metatheses of two different functional groups have been realized via (2+2) chemistry: e.g., carbonyl-isocyanate 25,26,94 and carbonyl-N-sulfinylamine metatheses. 25,95−97 Both examples showcase the feasibility of turning over early and middle TM-oxo intermediates through the respective formation of CO 2(g) or SO 2(g) (Figure 3D).…”

Section: Different Types Of (2+2) Metathesis Mechanisms Are Known As ...mentioning

confidence: 99%

Hetero-ene Metathesis

Johnson,

Zhukhovitskiy

2023

ACS Catal.

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Metathesis of double bonds has enabled innovation in a broad range of fields: from materials science to medicine. However, this chemistry has largely focused on alkenes rather than hetero-enes, or heteroatom-containing double bonds. Yet, the ability to do hetero-ene metathesis could grant access to valuable heteroatom-rich molecules. Catalysis of double bond metathesis has classically, though not exclusively, relied on the [2+2] cycloaddition/elimination mechanism, which in the case of olefins involves transition metal alkylidenes. However, this mechanism may not be ideal for some hetero-enes, nor is it uniquely suited for the purposes of metathesis: other mechanisms are feasible and, in some cases, precedented. In this Perspective, we present a general framework for mechanistic design that would apply to hetero-ene metathesis, with examples of reported transformations that justify this classification. Advantages, challenges, and opportunities within each class of mechanisms are also outlined. We hope that this Perspective will catalyze further research in this burgeoning field.

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Section: Different Types Of (2+2) Metathesis Mechanisms Are Known As ...mentioning

confidence: 99%

Hetero-ene Metathesis

Johnson,

Zhukhovitskiy

2023

ACS Catal.

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“…66%) [2] werden durch die Zugabe katalytischer M engen an Metallcarbonylen gem ildert und die A usbeute steigt auf 90% [3]. Für diese katalytische Bildung von Iminen wird aufgrund kinetischer Messungen ein fünfgliedri ger M etallacyclus als Zwischenstufe postuliert [4].…”

unclassified

“…Zur Erm ittlung der katalytischen Aktivität wurde, um vergleichbare, aussagekräftige Ergebnisse zu e r halten, unter den in Lit. [4] genannten Bedingungen gearbeitet. Dazu wurden als Edukte Phenylisocyanat Drapier et al [4] Nach der alternativen Reaktionsfolge b reagiert A mit dem Aldehyd 4 zu dem .T-Komplex 10 (isoliert mit z.…”

unclassified

“…[4] genannten Bedingungen gearbeitet. Dazu wurden als Edukte Phenylisocyanat Drapier et al [4] Nach der alternativen Reaktionsfolge b reagiert A mit dem Aldehyd 4 zu dem .T-Komplex 10 (isoliert mit z. B. Lig = TM ED A [13]).…”

unclassified

“…D ra pier et al [4] form ulieren einen Mechanismus, bei dem die Decarboxylierung zum Komplex 12 (isoliert mit Lig = TM E D A [15]) erfolgt, welcher nun unter Freisetzung des Imins 6 das (Lig)Ni°-System A rege neriert.…”

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Nickel(0)-katalysierte Synthese von Iminen aus Isocyanaten und Aldehyden/ Nickel(0) Catalysed Synthesis of Imines from Isocyanates and Aldehydes

Hoberg

Sümmermann

1984

Zeitschrift Für Naturforschung B

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Insertionsreaktionen mit Isocyanaten — Reaktionsmöglichkeiten, Kinetik, Mechanismen

Noack

Schwetlick

1987

Zeitschrift fuer Chemie

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The insertion reactions of isocyanates into CN, CO, CS, SiN, SiO, SiS, SiP, PN, PO, PM, BC, BN, BO, BS, BHal, SnN, SnO, SnS and other MX bonds are reviewed. Rate constants are in the range of 10−6 to 103 M−1 s−1, often above 10 M−1 s−1. Reaction mechanisms freguently involve equilibria prior to the rate determining step. Cyclisations to N‐heterocycles, uretdiones and isocyanurates and formation of carbodiimides are observed as side‐reactions. Ring expansions open routes to macrocyclic compounds. Insertions are important in organometal catalysis of isocyanate reactions as well as in metal complex catalyzed syntheses and, therefore, in a number of industrial processes.

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Metal carbonyls catalysed reaction of isocyanates with aldehydes

Cited by 12 publications

References 40 publications

Hetero-ene Metathesis

Hetero-ene Metathesis

Nickel(0)-katalysierte Synthese von Iminen aus Isocyanaten und Aldehyden/ Nickel(0) Catalysed Synthesis of Imines from Isocyanates and Aldehydes

Insertionsreaktionen mit Isocyanaten — Reaktionsmöglichkeiten, Kinetik, Mechanismen

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