2016
DOI: 10.1002/adsc.201600727
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Double Addition of Organometallics to Nitriles: Toward an Access to Tertiary Carbinamines

Abstract: As depicted in many textbooks, the addition of organometallics to nitriles is generally limited to a single addition, providing ketones after acidic hydrolysis. However, the double addition, leading to tertiary carbinamines is also possible, as demonstrated as early as 1939 by the double addition of allyl Grignard reagents to α‐ethoxyacetonitrile. Since this seminal result, and stimulated by the biological importance of the so‐obtained carbinamines, efforts were devoted to expand the scope of the double additi… Show more

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Cited by 40 publications
(13 citation statements)
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“…The use of very harsh conditions, microwave heating, and Lewis acids such as titanium alkoxides somewhat expanded the scope of the reaction so as to include two different organometallic nucleophiles and less reactive nitriles . Aside from some exceptions, however, chemical yields and selectivities were generally modest, and long reaction times (up to 24 h) were usually required for the second addition …”
Section: Methodsmentioning
confidence: 99%
“…The use of very harsh conditions, microwave heating, and Lewis acids such as titanium alkoxides somewhat expanded the scope of the reaction so as to include two different organometallic nucleophiles and less reactive nitriles . Aside from some exceptions, however, chemical yields and selectivities were generally modest, and long reaction times (up to 24 h) were usually required for the second addition …”
Section: Methodsmentioning
confidence: 99%
“…36 The introduction of a nitrile group was an important contribution to this field given the nitrile's ubiquity in natural products, pharmaceuticals, agrochemicals, and materials, 37,38 as well as its importance as a synthetic intermediate. [39][40][41] N-Cyanosuccinimide, an electrophilic cyanating reagent, was chosen as a way to avoid the use of toxic cyanide sources. 42,43 This reaction is mechanistically related to sequential Co(III)catalysed additions to dienes and carbonyl compounds because the nitrile group is introduced at the 3-position of the diene via a b-hydride elimination/reinsertion process to generate the reactive Co-allyl intermediate (Scheme 11(a)).…”
Section: Dienes As Coupling Partnersmentioning
confidence: 99%
“…Hence, the present protocolp rovides facile access to enantiomerically enriched a-quaternary malononitriles that can serve as starting point for variousfurther transformations. [22] To highlight the overall synthetic practicability of the present method,agram-scaler eaction was carriedo ut and 1.26 go f 3b were obtained with an enantiomeric ratio of 91:9 mirroring the results of the initial small-scale catalysis (Scheme 3). Besides its potentialasatransient acyl cyanide precursor,the ma- Table 2.…”
mentioning
confidence: 97%