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Synthesis 2005(19): 3355-3361  
DOI: 10.1055/s-2005-918453
PAPER
© Georg Thieme Verlag Stuttgart · New York

Conversion of Alkyl Halides into Alcohols via Formyloxylation Reaction with DMF Catalyzed by Silver Salts

Antonio Abad*, Consuelo Agulló, Ana C. Cuñat, Ismael Navarro
Departamento de Química Orgánica, Universidad de Valencia, Dr. Moliner 50, 46100-Burjassot, Valencia, Spain
Fax: +34(963)544328; e-Mail: antonio.abad@uv.es;
Further Information

Publication History

Received 11 May 2005
Publication Date:
28 October 2005 (online)

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Abstract

The transformation of alkyl halides into alcohols via a two-step process based on the reaction with DMF catalyzed by Ag(I) salts followed by acid or basic hydrolysis of the intermediate formate ester has been evaluated. The results show that a large variety of primary and some secondary alkyl halides can be transformed efficiently into the corresponding alcohols, making this alkyl halide to alcohol interconversion a valuable alternative to the existing procedures, particularly in molecules with labile functional groups that are generally involved in multistep synthesis.

Key words

alkyl halides - alcohols - catalysis - nucleophilic substitutions - eliminations

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19

We have isolated the intermediate imidate salt i (Figure [2] ), formed in the formyloxylation reaction of chlorocarvone 1, by work up of the reaction mixture under anhydrous conditions. This salt has been characterized by 1H, 19F, and 13C NMR. 1H NMR (CDCl3): δ = 8.61 (s, N=CH), 6.80 (m, H-3), 5.44 and 5.28 (2 s, =CH2), 5.19 (AB system, J = 13 Hz, CH2O), 3.46 and 3.24 [2 s, N(CH3)2], 1.78 (s, CH3-2). 19F NMR (CDCl3, 282 MHz): δ = -152.5. 13C NMR (CDCl3): δ = 198.9 (CO), 167.1 (N=C), 144.5 (C-3), 142.6 (C-2), 137.7 (C-1′), 119.0 (C-2′′), 79.9 (CH2O), 42.9 (C-6), 41.9 (C-5), 37.7 and 36.5 (Me2N= ), 30.9 (C-4), 15.6 (CH3-2).

21

The more reactive bromide 7 can be directly transformed into the corresponding alcohol by treatment with H2O-CH3NO2/AgBF4. However, the yield of this transformation is significantly lower than that obtained with the DMF-based procedure, due to the formation of substantial amounts of CH3 (CH2)9O(CH2)9CH3 (up to 25%).