CCCLVIII.—Action of the Grignard reagent upon amino-nitriles

Stevens, Thomas S.; Cowan, John Murdoch; MacKinnon, John

doi:10.1039/jr9310002568

Cited by 6 publications

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“…This reaction generally is encountered for -aminonitriles unsubstituted at the -carbon. [13][14][15][16][17][18] An example is provided in Scheme 2 on piperidine and pyrrolidine derivatives 1a-b. 19 The reaction leads to ketones 2a-b with small amounts of dimers 4a-b formed from deprotonation by the Grignard reagent followed by condensation on the cyano group.…”

Section: Reactivity Of Grignard Reagents Towards -Aminonitriles and ...mentioning

confidence: 99%

“…19 The reaction leads to ketones 2a-b with small amounts of dimers 4a-b formed from deprotonation by the Grignard reagent followed by condensation on the cyano group. 13,14,18 With a monosubstituted -carbon, the substitution often is the major pathway, [13][14][15][16][17][20][21][22][23][24] however, the addition was reported to be predominant in some cases. 16,21,22,25,26 Scheme 2.…”

Section: Reactivity Of Grignard Reagents Towards -Aminonitriles and ...mentioning

confidence: 99%

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The Bruylants and related reactions

Mattalia¹

2021

Arkivoc

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This review focuses on the Bruylants reaction, namely the substitution with Grignard reagents of the cyano group in -aminonitriles. This reaction goes through an iminium ion intermediate and proceeds with excellent stereoselectivities. The extension to organozinc reagents has been successfully applied. Triazoles such as benzotriazole and especially 1,2,3-triazole appear as relevant substitutes for the cyano leaving group. An alternative pathway for substitution of the cyano group involves an -alkylation-decyanation sequence. Selected applications in organic synthesis are proposed.

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