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Synlett 2010(16): 2429-2434  
DOI: 10.1055/s-0030-1258552
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Exceptionally Active Catalysts for the Formation of Carbamates from Alcohols and Isocyanates: Molybdenum(VI) Dichloride Dioxide and Its DMF Complex

Christian Stock, Reinhard Brückner*
Institut für Organische Chemie und Biochemie, Albert-Ludwigs-Universität, Albert-Str. 21, 79104 Freiburg, Germany
Fax: +49(761)2036100; e-Mail: reinhard.brueckner@organik.chemie.uni-freiburg.de;
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Publikationsverlauf

Received 21 June 2010
Publikationsdatum:
03. September 2010 (online)

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Abstract

Small amounts of MoO2Cl2 or MoO2Cl2(DMF)2 catalyze carbamate formation from an alcohol and isocyanates: 0.1 mol% of the respective additive allow primary, secondary or tertiary alcohols to add to aliphatic or aromatic isocyanates of varied steric hindrance within 20 minutes at room temperature. Typically the corresponding carbamate resulted in 100% yield. Only particularly hindered substrates required 1.0 mol% of the catalyst while as little as 0.01% sufficed for the phenylcarbamoylation of menthol. Catalytic amounts of DMAP accelerate carbamate formation from certain alcohols and isocyanates, too.

Key words

addition - carbamoylation - DMAP - heterocumulene - urethane formation

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53

Typical Procedure for the Carbamoylation of Alcohols with Isocyanates: At 22 ˚C neat benzyl isocyanate (31; 0.52 mL, 0.56 g, 1.1 equiv) was added to MoO2Cl2(DMF)2 (1.3 mg, 3.8 µmol, 0.1 mol%) and 1.0 M (-)-menthol (16; 594 mg, 3.80 mmol) in CH2Cl2 (3.8 mL). The mixture was stirred at r.t. for 20 min. CH2Cl2 (10 mL) and H2O (7 mL) were added. The aqueous phase was extracted with CH2Cl2 (2 × 12 mL). The combined organic phases were dried over Na2SO4. Removal of the solvent under reduced pressure gave N-benzyl-O-[(1R,2S,5R)-2-isopropyl-5-methylcyclo-hexyl] carbamate (35; 1.10 g, 100%) as a white solid (mp 92 ˚C). It was a pure compound as evidenced by ¹H NMR spectroscopy and combustion analysis.

55

All new compounds (12, 15, 36, and 37) gave satisfactory ¹H NMR and ¹³C NMR spectra and correct combustion analyses for C, H, and N (±0.30%). Analytical details will be published in a full paper in due course.