The Reductive Decyanation Reaction: Chemical Methods and Synthetic Applications

Mattalia, Jean-Marc Robert; Marchi-Delapierre, Caroline; Hazimeh, Hassan; Chanon, Michel

doi:10.1002/chin.200632272

Cited by 8 publications

(7 citation statements)

References 1 publication

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“…[11][12][13][14][15][16] C-Alkylation of deprotonated unprotected aminonitriles 1 affords α-branched products 2, from which HCN can be eliminated to form ketimines 3. [17] Depending on the structure of the compound 3, this elimination may occur spontaneously. Hydrolysis of imines 3 produces ketones, while their reduction furnishes α-branched amines 4.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of (–)‐(S)‐Norlaudanosine, (+)‐(R)‐O,O‐Dimethylcoclaurine, and (+)‐(R)‐Salsolidine by Alkylation of an α‐Aminonitrile

2007

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Section: Introductionmentioning

confidence: 99%

Synthesis of (–)‐(S)‐Norlaudanosine, (+)‐(R)‐O,O‐Dimethylcoclaurine, and (+)‐(R)‐Salsolidine by Alkylation of an α‐Aminonitrile

2007

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“…Serendipitous reductive decyanation during the methylation of 1. [4][5][6][7] and could be useful as an ew protocol with ad istinct reaction mechanism. Therefore,w e next examined the scope of the decyanation of carbonitriles under these reaction conditions (Scheme 2).…”

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confidence: 99%

Hydride Reduction by a Sodium Hydride–Iodide Composite

et al. 2016

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Sodium hydride (NaH) is widely used as aBrønsted base in chemical synthesis and reacts with various Brønsted acids,whereas it rarely behaves as areducing reagent through delivery of the hydride to polar p electrophiles.T his study presents aseries of reduction reactions of nitriles,amides,and imines as enabled by NaH in the presence of LiI or NaI. This remarkably simple protocol endows NaH with unprecedented and unique hydride-donor chemical reactivity.Hydridereductionofpolarp electrophiles,such as carbonyl compounds,c arbonitriles,a nd imines,i so ne of the most fundamental and important molecular transformations in chemical synthesis.[1] In this context, av ariety of covalent hydrides,s uch as borane,a lane,m etal borohydrides,m etal aluminum hydrides,and silanes,have often been employed as the reagents of choice for stereo-, regio-, and chemoselective hydride-transfer processes.Bycontrast, alkali-metal hydrides have rarely been employed as hydride sources;i nstead, they are used almost exclusively as strong Brønsted bases for deprotonation reactions in chemical synthesis. [2,3] Herein, we report that NaH can act as ahydride donor in reactions with nitriles,a mides,a nd imines when it has been subjected to simple solvothermal treatment with LiI or NaI in THF.O f particular interest is the outcome of hydride reduction reactions of nitriles and amides,w hich deliver the corresponding alkanes (through decyanation) and aldehydes, respectively.During the course of our experiments on the a-methylation of diphenylacetonitrile (1)t op repare tertiary carbonitrile 2a,weinvestigated its reaction with NaH (3 equiv) and MeI (1.2 equiv) in THF (85 8 8Ci nas ealed tube;S cheme 1). Although the desired tertiary nitrile 2a was isolated in 74 % yield, we were surprised to observe the formation of 1,1-diphenylethane (3a)i n2 5% yield as aside product. Assuming that 3a was formed by the decyanation of nitrile 2a,w e expected that this decyanation reaction could be generalized to am ore versatile synthetic strategy

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“…The nitrile group undergoes reduction with many reducing agents. Depending on the nature of the reducing agent and experimental conditions, the reaction can produce amines, aldehydes, primary alcohols, imines, or alkanes [6,7]. In pursuit of the methods for synthesis of analogs of the key intermediate, 1-(cyano-(4-methoxyphenyl)methyl)-cyclohexanol, we have synthesized the title compound under mild conditions.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Crystal Structure of 1-(Cyano(4-methoxyphenyl)methyl)cyclohexyl Acetate

Mantelingu

Kavitha

Rangappa

et al. 2007

Molecular Crystals and Liquid Crystals

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The title compound, C 17 H 21 NO 3 , was synthesized by the acetylation of the hydroxy group of 1-(cyano(4-methoxyphenyl)methyl)cyclohexanol, which was formed by the reaction of 4-methoxyphenyl acetonitrile with cyclohexanone. The compound was characterized spectroscopically, and the structure was investigated by X-ray crystallography. The compound crystallizes in the orthorhombic crystal class in the space group Pbca with cell parameters a ¼ 13.412(6) Å , b ¼ 12.398(14) Å , c ¼ 19.026(19) Å , and V ¼ 3164(5) Å 3 for Z ¼ 8. The cyclohexane ring is in a chair conformation. The structure exhibits intermolecular hydrogen bonds of the type C-HÁ Á ÁN and C-HÁ Á ÁO.

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The Reductive Decyanation Reaction: Chemical Methods and Synthetic Applications

Abstract: ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Cited by 8 publications

References 1 publication

Synthesis of (–)‐(S)‐Norlaudanosine, (+)‐(R)‐O,O‐Dimethylcoclaurine, and (+)‐(R)‐Salsolidine by Alkylation of an α‐Aminonitrile

Synthesis of (–)‐(S)‐Norlaudanosine, (+)‐(R)‐O,O‐Dimethylcoclaurine, and (+)‐(R)‐Salsolidine by Alkylation of an α‐Aminonitrile

Hydride Reduction by a Sodium Hydride–Iodide Composite

Synthesis and Crystal Structure of 1-(Cyano(4-methoxyphenyl)methyl)cyclohexyl Acetate

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