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Synlett 2003(15): 2386-2388  
DOI: 10.1055/s-2003-42116
LETTER
© Georg Thieme Verlag Stuttgart · New York

Mild Two-Step Conversion of Primary Amides to Alcohols by Reduction of Acylimidodicarbonates with Sodium Borohydride

Ulf Ragnarsson*a, Leif Grehna, Luis S. Monteirob, Hernani L.S. Maiab
a Department of Biochemistry, University of Uppsala, Biomedical Center, PO Box 576, SE-751 23 Uppsala, Sweden
Fax: +46(18)552139; e-Mail: urbki@bmc.uu.se;
b Departamento de Quimica, Universidade do Minho, Gualtar, P-4700-320 Braga, Portugal
Further Information

Publication History

Received 8 September 2003
Publication Date:
07 November 2003 (online)

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Abstract

Di-tert-butyl acylimidodicarbonates, prepared from primary amides with two equivalents of di-tert-butyl dicarbonate under catalysis by 4-dimethylaminopyridine, readily undergo selective reductive cleavage of their acyl CO-N bonds by NaBH4 to provide the corresponding alcohols in high yields.

Key words

alcohols - amides - cleavage - reductions - sodium borohydride

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9

Typical Reduction Procedure: A solution of 2c (732 mg, 2 mmol) in abs EtOH (12 mL) was treated with an excess of NaBH4 (151 mg, 4 mmol) in one batch. After 20 h, when all starting material had been consumed (TLC monitoring), acetone (1 mL) was added, whereupon after 1 h the solvent was evaporated. The obtained foam was dissolved in Et2O/H2O, the aqueous phase backwashed once with Et2O and the combined extracts dried (Na2SO4). After evaporation the mixture was purified by chromatography on silica gel (eluent: Et2O/CH2Cl2 1:15). HNBoc2 eluted first, followed by pure 3c (298 mg, 97%); mp 91-92 °C; it was recrystallized from Et2O/light petroleum.