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)

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.

    References and Notes

  • For polyurethane reviews, see:
  • 1a Silva AL. Bordado JC. Catal. Rev.  2004,  46:  31 
  • 1b Moratti SC. Charalambides YC. ‘Polymeric Carbamic Acids and Esters, and Their Sulfur Analogues’, in ‘Four Carbon-Heteroatom Bonds: X-C≡X, X=C=X, X2C=X, CX4’, Science of Synthesis, Houben-Weyl Methods of Organic Chemistry   Vol. 18:  Knight JG. Thieme; Stuttgart / New York: 2005.  p.649-664  
  • 2 For example: Propamocarb and Carbaryl: Römpp Online   Version 3.1:  Georg Thieme Verlag; Stuttgart: 2008. 
  • 3a Rivastigmine: Winblad B. Grossberg G. Frölich L. Farlow M. Zechner S. Nagel J. Lane R. Neurology  2007,  69:  14 
  • 3b Retigabine: Blackburn-Munro G. Dalby-Brown W. Mirza NR. Mikkelsen JD. Blackburn-Munro RE. CNS Drug Rev.  2005,  11:  1 
  • 3c Pardoprunox: Hauser RA. Bronzova J. Sampaio C. Lang AE. Rascol O. Theeuwes A. van de Witte SV. Eur. Neurol.  2009,  62:  40 
  • 4 Snieckus V. Chem. Rev.  1990,  90:  879 
  • 5a Hoppe D. Hense T. Angew. Chem., Int. Ed. Engl.  1997,  36:  2282 ; Angew. Chem., 1997, 109, 2376
  • 5b Beak P. Johnson TA. Kim DD. Lim SH. Organolithiums in Enantioselective Synthesis In Top. Organomet. Chem.   Vol. 5:  Hodgson DM. 2003.  p.139-176  
  • 6a Evans DA. Aldrichimica Acta  1982,  15:  23 
  • 6b Ager DJ. Prakash I. Schaad DR. Chem. Rev.  1996,  96:  835 
  • 6c Sibi MP. Aldrichimica Acta  1999,  32:  93 
  • For carbamate reviews, see:
  • 7a Rossi L. in ‘Four Carbon-Heteroatom Bonds: X-C≡X, X=C=X, X2C=X, CX4’, Science of Synthesis, Houben-Weyl Methods of Organic Chemistry   Vol. 18:  Knight JG. Thieme; Stuttgart / New York: 2005.  p.461-648  
  • 7b Chaturvedi D. Mishra N. Mishra V. Curr. Org. Synth.  2007,  4:  308 
  • 8 Hutton CA. Bartlett PA. J. Org. Chem.  2007,  72:  6865 
  • 9 Nikiforov A. Jirovetz L. Buchbauer G. Liebigs Ann. Chem.  1989,  489 
  • 10 Varie DL. Beck C. Borders SK. Brady MD. Cronin JS. Ditsworth TK. Hay DA. Hoard DW. Hoying RC. Linder RJ. Miller RD. Moher ED. Remacle JR. Rieck JA. Anderson DD. Dodson PN. Forst MB. Pierson DA. Turpin JA. Org. Process Res. Dev.  2007,  11:  546 
  • 11 Tsuji T. Nishida S. Okuyama M. Osawa E. J. Am. Chem. Soc.  1995,  117:  9804 
  • 12 Elman B. Moberg C. Tetrahedron  1986,  42:  223 
  • 13 Keyes RF. Carter JJ. Zhang X. Ma Z. Org. Lett.  2005,  7:  847 
  • 14 Cameron JF. Willson CG. Fréchet JMJ. J. Chem. Soc., Perkin Trans. 1  1997,  2429 
  • 15 Andrade RB. Martin SF. Org. Lett.  2005,  7:  5733 
  • 16 Duggan MI. Imagire JS. Synthesis  1989,  131 
  • 17 Nishikawa T. Urabe D. Tomita M. Tsujimoto T. Iwabuchi T. Isobe M. Org. Lett.  2006,  8:  3263 
  • 18 Paleo MR. Calaza MI. Sardina FJ. J. Org. Chem.  1997,  62:  6862 
  • 19 Cameron JF. Fréchet JMJ. J. Org. Chem.  1990,  55:  5919 
  • 20 Cate AT. Dankers PYW. Kooijman H. Spek AL. J. Am. Chem. Soc.  2003,  125:  6860 
  • 21 Dillard RD. Poore GA. Easton NR. Sweeney MJ. Gibson WR. J. Med. Chem.  1968,  11:  1155 
  • 22 Spino C. Joly M.-A. Godbout C. Arbour M. J. Org. Chem.  2005,  70:  6118 
  • 23 Benalil A. Roby P. Carboni B. Vaultier M. Synthesis  1991,  787 
  • 24 Villhauer EB. Brinkman JA. Naderi GB. Burkey BF. Dunning BE. Prasad K. Mangold BL. Russell ME. Hughes TE. J. Med. Chem.  2003,  46:  2774 
  • 25a Britain JW. Gemeinhardt PG. J. Appl. Polym. Sci.  1960,  4:  207 
  • 25b Francis T. Thorne MP. Can. J. Chem.  1976,  54:  24 
  • 26 White DK. Greene FD. J. Org. Chem.  1978,  43:  4530 
  • 27 Kim YH. Park HS. Synlett  1998,  261 
  • 28 Hodgson DM. Thompson AJ. Wadman S. Keats CJ. Tetrahedron  1999,  55:  10815 
  • 29 Finke PE. Oates B. Mills SG. MacCoss M. Malkowitz L. Springer MS. Gould SL. DeMartino JA. Carella A. Carver G. Holmes K. Danzeisen R. Hazuda D. Kessler J. Lineberger J. Miller M. Schleif WA. Emini EA. Bioorg. Med. Chem. Lett.  2001,  11:  2475 
  • 30 Review: Jeyakumar K. Chand DK. J. Chem. Sci.  2009,  121:  111 
  • 31 Jeyakumar K. Chand DK. Synthesis  2009,  306 
  • 32 Jeyakumar K. Chand DK. Synthesis  2008,  807 
  • 33 Jeyakumar K. Chand DK. Synthesis  2008,  1685 
  • 34 Weng S.-S. Lin Y.-D. Chen C.-T. Org. Lett.  2006,  8:  5633 
  • 35 Goswami S. Maity AC. Tetrahedron Lett.  2008,  49:  3092 
  • 36 Chen C.-T. Kuo J.-H. Pawar VD. Munot YS. Weng S.-S. Ku C.-H. Liu C.-Y. J. Org. Chem.  2005,  70:  1188 
  • 37a Fernandes AC. Fernandes R. Romão CC. Royo B. Chem. Commun.  2005,  213 
  • 37b Reis PM. Romão CC. Royo B. Dalton Trans.  2006,  1842 
  • 38 Fernandes AC. Romão CC. Tetrahedron Lett.  2005,  46:  8881 
  • 39 Fernandes AC. Romão CC. J. Mol. Catal. A: Chem.  2006,  253:  96 
  • 40 Fernandes AC. Romão CC. J. Mol. Catal. A: Chem.  2007,  272:  60 
  • 41a Fernandes AC. Romão CC. Tetrahedron  2006,  62:  9650 
  • 41b Sanz R. Escibano J. Fernández Y. Aguado R. Pedrosa MR. Arnáiz FJ. Synlett  2005,  1389 
  • 43a Sanz R. Escibano J. Aguado R. Pedrosa MR. Arnáiz FJ. Synthesis  2004,  1629 
  • 43b Fernandes AC. Romão CC. Tetrahedron Lett.  2007,  48:  9176 
  • 44 Jeyakumar K. Chand DK. Tetrahedron Lett.  2006,  47:  4573 
  • 45 Sanz R. Escibano J. Pedrosa MR. Aguado R. Arnáiz FJ. Adv. Synth. Catal.  2007,  349:  713 
  • 46 Note added in proof: During revision of our manuscript MoO2Cl2(DMF)2 catalysis in reductive cyclizations of (ortho-nitroaryl)alkenes was reported by: Malakar CC. Merisor E. Conrad J. Beifuss U. Synlett  2010,  1766 
  • 47 Sanz R. Aguado R. Pedrosa MR. Arnáiz FJ. Synthesis  2002,  856 
  • 48 Arnáiz FJ. Aguado R. Martinez de Ilarduya JM. Polyhedron  1994,  13:  3257 
  • 49 Jeyakumar K. Chand DK. Appl. Organomet. Chem.  2006,  20:  840 
  • 50a Bruno SM. Balula SS. Valente AA. Almeida Paz FA. Pillinger M. Sousa C. Klinowski J. Freire C. Ribeiro-Claro P. Gonçalves IS. J. Mol. Catal. A: Chem.  2007,  270:  185 
  • 50b Bruno SM. Pereira CCL. Balula MS. Nolasco M. Valente AA. Hazell A. Pillinger M. Ribeiro-Claro P. Gonçalves IS. J. Mol. Catal. A: Chem.  2007,  261:  79 
  • 50c Bruno SM. Fernandes JA. Martins LS. Gonçalves IS. Pillinger M. Ribeiro-Claro P. Rocha J. Valente AA. Catal. Today  2006,  114:  263 
  • 51 Salles L. Nixon AF. Russell NC. Clarke R. Pogorzelec P. Cole-Hamilton DJ. Tetrahedron: Asymmetry  1999,  1471 
  • 52 Still WC. Kahn M. Mitra A. J. Org. Chem.  1978,  43:  2923 
  • 54a

    Carbamates 12, 15, 36, and 37 are new compounds.55 Other carbamates were described (inter alia) in the following references:

  • 54b Gautschi M. inventors; WO Patent,  2004/000023A1. Carbamates 17 and 34:
  • 54c Carbamate 24: Leogane O. Lebel H. Synthesis  2009,  1935 
  • 54d Seemayer R, and Liang J. inventors; WO Patent,  2004/037827A1. Carbamate 25:
  • 54e Carbamates 26 and 29: Newton R. Savage GP. Aust. J. Chem.  2008,  61:  432 
  • 54f Carbamate 27: Wiberg KB. Wang Y.-G. Miller SJ. Puchlopek ALA. J. Org. Chem.  2009,  74:  3659 
  • 54g Carbamate 28: Steinke T. Shaw BK. Jong H. Patrick BO. Fryzuk MD. Organometallics  2009,  28:  2830 
  • 54h Carbamate 35: Martínez R. Ramón DJ. Yus M. Adv. Synth. Catal.  2008,  350:  1235 
  • 54i Kroetz DL, Zeldin DC, Hammock BD, and Morisseau C. inventors; US Patent,  6531506B1. Carbamate 38:
  • 54j Boghani N, and Gebreselassie P. inventors; WO Patent,  2006/127738A2. Carbamate 39:
  • 54k Carbamate 40: Heydari A. Khaksar S. Tajbakhsh M. Synthesis  2008,  3126 
42

Cf. ref. 41a.

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.