The reductive decyanation reaction: an overview and recent developments

Mattalia, Jean-Marc Robert

doi:10.3762/bjoc.13.30

Cited by 50 publications

(26 citation statements)

References 140 publications

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“…Selective removal of a specific functional group after fully utilizing its beneficial aspects is a well known strategy in synthetic chemistry [9] . In this regard, nitrile or cyano group is generally considered as one of the most difficult functionalities to remove from a molecule [10] . Recent progress in synthetic chemistry has at least empowered chemists with some options for selective removal of the nitrile group.…”

Section: Hydrodecyanationmentioning

confidence: 99%

Recent Developments in Hydrodecyanation and Decyanative Functionalization Reactions

Paul

Patra

2021

Asian J Org Chem

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Nitrile is one of the ubiquitous functional groups in natural products and polymer industry. It is often used as a versatile building block in synthetic chemistry. Classically, nitrile group is used for alpha functionalization, orthoÀ CÀ H activation and as a precursor for amine or carbonyl functionalities. With the development of various transition metal catalyzed methods, in the last two decades, nitrile group has emerged as a source of carbon synthons through CÀ CN bond activation despite of its high bond energy. In this review we have summarized all recent developments involving the carbon synthons arising from the cleavage of CÀ CN bonds. Depending on the fate of the carbon center after cleavage, all the reactions are classified in two major categories for the ease of discussion: 1) decyanation (removal of the nitrile group) and 2) decyanative functionalization (replacement of the nitrile group). Finally, current limitations in CÀ CN bond activation strategies and future prospects are discussed.

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Section: Hydrodecyanationmentioning

confidence: 99%

Recent Developments in Hydrodecyanation and Decyanative Functionalization Reactions

Paul

Patra

2021

Asian J Org Chem

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“…This is particularly the case with insoluble metal cyanides, such as NaCN and KCN, when reactions are performed in organic solvents. Nevertheless, the obtained organonitriles are ubiquitous functional group in organic synthesis, enabling facile synthesis of various molecular scaffolds via meta-selective C-H activation [6,7], reduction (amines) [8], hydrolysis (carbonyls) [9], radical reactions (cyanide abstraction) [10,11] and umpolung chemistry (cyanohydrins) [12]. Among many reaction pathways, hydrocyanation with gaseous HCN showed the most atom economic reaction with olefin substrates [13].…”

Section: Introductionmentioning

confidence: 99%

A CO2-Mediated Conjugate Cyanide Addition to Chalcones

et al. 2020

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Carbon dioxide is an intrinsically stable molecule; however, it can readily react with various nucleophilic reagents. In the presence of a cyanide source, CO2 was proven to be useful to promote addition reactions. Here we report the use of CO2 to facilitate 1,4-conjugate cyanide addition reaction to chalcones to generate organonitriles. Nitriles are key component in organic synthesis due to their utility in numerous functional group transformation, however, conjugation addition of cyanide has been a challenge in this substrate class due to side reactions. To mitigate this, we employed simple ammonium and metal cyanide sources as nucleophiles under carbon dioxide atmosphere where high selectivity toward the desired product was obtained. The presented reaction is not feasible under inert atmosphere, which highlights the important role of CO2, as a Lewis and Brøndsted acidic catalyst. Further derivatization of organonitriles compounds were performed to showcase the utility of the reaction, while an unprecedented dimerization reaction was identified and characterized, affording a cyclopentanone scaffold.

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“…1 For example, they can undergo conjugate addition [2][3][4][5] or reduction 6,7 to yield alkylmalononitriles. In turn, alkylmalononitriles can be processed to malonic acid derivatives, 8 reduced to 1,3-diamines, 9,10 and undergo reductive 11,12 and oxidative decyanation reactions. [13][14][15][16][17][18] Most relevant to this work, Hayashi and co-workers developed an elegant oxidative protocol to convert malononitriles into amides or esters using molecular oxygen as the oxidant via the intermediacy of an acylcyanide (Scheme 1A).…”

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confidence: 99%

Functional Group Interconversion of Alkylidenemalononitriles to Primary Alcohols by a Cooperative Redox Operation

Emmetiere

Grenning²

2020

Synthesis

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Functional group interconversions are essential chemical processes enabling synthesis. In this report, we describe a strategy to convert alkylidenemalononitriles into primary alcohols in one step. The reaction relies on a choreographed redox process involving alkylidene reduction, malononitrile oxidation, and acylcyanide reduction where molecular oxygen and NaBH4 work cooperatively. The method was applied to a variety of carbon skeletons and was utilized to synthesize complex terpenoid architectures.

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The reductive decyanation reaction: an overview and recent developments

Cited by 50 publications

References 140 publications

Recent Developments in Hydrodecyanation and Decyanative Functionalization Reactions

Recent Developments in Hydrodecyanation and Decyanative Functionalization Reactions

A CO2-Mediated Conjugate Cyanide Addition to Chalcones

Functional Group Interconversion of Alkylidenemalononitriles to Primary Alcohols by a Cooperative Redox Operation

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