Synthesis of Urea and Carbamate Glycosides Employing Unprotected Carbohydrates

Abstract

A study of methods for the synthesis of urea and carbamate glycosides, starting with unprotective carbohydrates, led to the preparation of amino acid-carbohydrate conjugates in aqueous ­media.

neoglycoconjugates - urea - carbamate - glucose - glucosamine

References and Notes

<A NAME="RU02511ST-1A">1a</A> Davis BG. J. Chem. Soc., Perkin Trans. 1  1999,  3215 

<A NAME="RU02511ST-1B">1b</A> Gamblin DP. Scanlan EM. Davis BG. Chem. Rev.  2009,  109:  131 

<A NAME="RU02511ST-2A">2a</A> Ichikawa Y. Nishiyama T. Isobe M. Synlett  2000,  1256 

<A NAME="RU02511ST-2B">2b</A> Ichikawa Y. Nishiyama T. Isobe M. J. Org. Chem.  2001,  66:  4200 

<A NAME="RU02511ST-2C">2c</A> Nishiyama T. Ichikawa Y. Isobe M. Synlett  2003,  47 

<A NAME="RU02511ST-2D">2d</A> Ichikawa Y. Matsukawa Y. Nishiyama T. Isobe M. Eur. J. Org. Chem.  2004,  586 

<A NAME="RU02511ST-2E">2e</A> Ichikawa Y. Nishiyama T. Isobe M. Tetrahedron  2004,  60:  2621 

<A NAME="RU02511ST-2F">2f</A> Ichikawa Y. Ohara F. Kotsuki H. Nakano K. Org. Lett.  2006,  8:  5009 

<A NAME="RU02511ST-3A">3a</A> Dobashi K. Nagaoka K. Watanabe Y. Nishida M. Hamada M. Takeuchi T. Umezawa H. J. Antibiot.  1985,  1166 

<A NAME="RU02511ST-3B">3b</A> Ellestad GA. Cosulich DB. Broschard RW. Martin JH. Kunstmann MP. Morton GO. Lancaster JE. Fulmor W. Lovell FM. J. Am. Chem. Soc.  1978,  100:  2515 

For synthetic works, see:

<A NAME="RU02511ST-3C">3c</A> Nishiyama T. Isobe M. Ichikawa Y. Angew. Chem. Int. Ed.  2005,  44:  4372 

<A NAME="RU02511ST-3D">3d</A> Nishiyama T. Kusumoto Y. Okumura K. Hara K. Kusaba S. Hirata K. Kamiya Y. Isobe M. Nakano K. Ichikawa Y. Chem. Eur. J.  2010,  16:  600 

<A NAME="RU02511ST-4A">4a</A> Ichikawa Y. Matsukawa Y. Isobe M. Synlett  2004,  1019 

<A NAME="RU02511ST-4B">4b</A> Ichikawa Y. Matsukawa Y. Isobe M. J. Am. Chem. Soc.  2006,  128:  3934 

<A NAME="RU02511ST-4C">4c</A> Ichikawa Y. Matsukawa Y. Tamura M. Ohara F. Isobe M. Kotsuki H. Chem. Asian J.  2006,  1:  717 

<A NAME="RU02511ST-5A">5a</A> Fisher E. Ber.  1914,  47:  1377 

<A NAME="RU02511ST-5B">5b</A> Bannister B. J. Antibiot.  1972,  377 

<A NAME="RU02511ST-5C">5c</A> Pinter I. Kovacs J. Toth G. Carbohydr. Res.  1995,  273:  99 

<A NAME="RU02511ST-5D">5d</A> Bottcher C. Burger K. Tetrahedron Lett.  2003,  44:  4223 

<A NAME="RU02511ST-5E">5e</A> Prosperi D. Ronchi S. Lay L. Rencurosi A. Russo G. Eur. J. Org. Chem.  2004,  395 

<A NAME="RU02511ST-5F">5f</A> Prosperi D. Ronchi S. Panza L. Rencurosi A. Russo G. Synlett  2004,  1529 

<A NAME="RU02511ST-5G">5g</A> Bianchi A. Ferrario D. Bernardi A. Carbohydr. Res.  2006,  341:  1438 

<A NAME="RU02511ST-5H">5h</A> Sawada D. Sasayama S. Takahashi H. Ikegami S. Tetrahedron Lett.  2006,  47:  7219 

<A NAME="RU02511ST-5I">5i</A> Yang J. Mercer GJ. Nguyen HM. Org. Lett.  2007,  9:  4231 

<A NAME="RU02511ST-5J">5j</A> Sawada D. Sasayama S. Takahashi H. Ikegami S. Tetrahedron  2008,  64:  8780 

<A NAME="RU02511ST-5K">5k</A> Mercer GJ. Yang J. McKay MJ. Nguyen HM. J. Am. Chem. Soc.  2008,  130:  11210 

<A NAME="RU02511ST-5L">5l</A> For a review, see: Spanu P. Ulgheri F. Curr. Org. Chem.  2008,  12:  1071 

<A NAME="RU02511ST-6A">6a</A> Schoorl MN. Recl. Trav. Chim. Pays-Bas  1903,  22:  31 

<A NAME="RU02511ST-6B">6b</A> Benn MH. Jones AS. J. Chem. Soc.  1960,  3837 

<A NAME="RU02511ST-7">7</A> Helferich B. Kosche W. Ber.  1926,  59:  69 

<A NAME="RU02511ST-8">8</A> Ercikson JG. Keps JS. J. Am. Chem. Soc.  1953,  75:  4339 

<A NAME="RU02511ST-9">9</A> Ichikawa Y. Watanabe H. Kotsuki H. Nakano K. Eur. J. Org. Chem.  2010,  6331 

<A NAME="RU02511ST-10">10</A>

A solution of d-glucose (300 mg, 1.67 mmol) and 1-n-butylurea (387 mg, 3.33 mmol) in a mixture of 2.4 M HCl (0.25 mL) and MeCN (1.0 mL) was stirred at 50 ˚C for 24 h. The mixture was neutralized by the addition of NaHCO₃ and washed with CH₂Cl₂ to remove excess 1-n-butylurea. The resulting aqueous layer was extracted with n-butanol. The combined n-butanol extracts were concentrated under reduced pressure to afford the crude 1-n-butyl-3-glucosyl-urea, which was treated with a mixture of acetic anhydride (5.0 mL) and pyridine (10 mL) at 50 ˚C for 3 h. After standard workup followed by chromatographic purification, a mixture of acetyl β-1-n-butyl-3-glucosylurea and acetyl
α-1-n-butyl-3-glucosylurea 12 (507 mg, β/α = 92:8) was obtained in 68% yield. Concentration of CH₂Cl₂ extracts and purification by chromatography provided the recovered 1-n-butylurea (210 mg). The yield of 1-n-butyl-3-glucosylureas 12 based on the consumed 1-n-butylurea was calculated to be 75%.

<A NAME="RU02511ST-11">11</A> Ichikawa Y. Morishita Y. Kusaba S. Sakiyama N. Matsuda Y. Nakano K. Kotsuki H. Synlett  2010,  1815 

<A NAME="RU02511ST-12">12</A>

Urea glucosamide 23 was reported to be synthesized from isonitrile 26 prepared from N-acetyl-d-glucosamine 22 in five steps (Scheme  [9] ). See reference 2f.

Scheme 9

<A NAME="RU02511ST-13">13</A>

These types of N-glycosyl carbamates were synthesized by the reaction of glycosyl isocyanates with alcohols. Authentic samples of 24 and 25 were prepared by the reaction of n-butyl alcohol with glucosyl isocyanates, generated from glucosyl isonitriles 5 and 8. See reference 2d.