[825-28-5]  · C9H16N2  · 2-(2,6-Dimethylpiperidino)acetonitrile  · (MW 152.27)

(a-lithiation affords a formyl anion equivalent)

Physical Data: bp 99-102 °C/15 mmHg.1

Preparative Method: by the condensation of 2,6-dimethylpiperidine and Chloroacetonitrile.1

One-Carbon Homologation of Alkyl Halides to Aldehydes.

Following deprotonation, this latent formyl anion equivalent -CHO can be alkylated with alkyl halides and then hydrolyzed to the homologous aldehyde or ethanolyzed to the acetal (eq 1).2

Synthesis of Aromatic Compounds.

Alkyl halides containing an electron-rich aromatic ring undergo subsequent cyclization via an iminium intermediate (eq 2).2

Formylation of a,b-Unsaturated Ketones.

Michael addition to 2-cyclohexen-1-one followed by reduction and methanolysis yields a hydroxy acetal derivative (eq 3).3

Related Reagents.

N,N-Diethylaminoacetonitrile; N,N-Dimethyldithiocarbamoylacetonitrile; (4aR)-(4aa,7a,8ab)-Hexahydro-4,4,7-trimethyl-4H-1,3-benzoxathiin; 2-Lithio-1,3-dithiane; Methoxyacetonitrile; Nitromethane; 1,1,3,3-Tetramethylbutyl Isocyanide; p-Tolylsulfonylmethyl Isocyanide; 2-(Trimethylsilyl)thiazole.

1. F. Hoffmann-La Roche & Co., Neth. Appl. 6 409 619, 1965 (CA 1965, 63, 2960g).
2. Wakamatsu, T.; Kondo, J.; Hobara, S.; Ban, Y. H 1982, 19, 481.
3. Wakamatsu, T.; Hobara, S.; Ban, Y. H 1982, 19, 1395.

Martin J. O'Donnell

Indiana University-Purdue University at Indianapolis, IN, USA

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