Novel Carbohydrate-Based Mono- and Bidentate Oligosilyl Ethers

Abstract

Regioselective one-pot O-silylation reactions of 1,2-O-isopropylidene-α-d-glucofuranose and 1,2-O-isopropylidene-β-d-fructopyranose using bulky oligosilyl groups are described. Some new silylating reagents (oligosilyl bistriflates), which were generated in situ from readily available phenylsilanes, resulted in 5,6-O-(glucofuranose) and 4,5-O-bridged (fructopyranose) carbohydrates with favoured seven- and eight-membered rings. In these cyclic oligosilyl diethers, three and four ring atoms, respectively, are Si atoms. It is noteworthy, that the seven-membered ring of 5,6-O-[2,4-bis(trimethylsilyl)-1,1,1,3,3,5,5,5-octamethylpentasilan-2,4-diyl]-1,2-O-isopropylidene-α-d-glucofuranose was expanded to an eight-membered ring by regioselective insertion of aerial oxygen into one of the Si-Si bonds. X-ray analyses of some derivatives are presented.

silyl triflates - bridging protecting groups - carbohydrates - hydrodesilylation

References

<A NAME="RT04406SS-1">1</A> Lalonde M. Chan TH. Synthesis  1985,  817 

<A NAME="RT04406SS-2">2</A> Greene T. Wuts PGM. Protecting Groups in Organic Synthesis   2nd ed.:  Wiley; New York: 1991. 

<A NAME="RT04406SS-3">3</A> Koncieński PJ. Protecting Groups   Thieme; Stuttgart: 1994. 

<A NAME="RT04406SS-4">4</A> Van Look G. Simchen G. Heberle J. Silylating Agents   Fluka; Buchs, Switzerland: 1995. 

<A NAME="RT04406SS-5">5</A> Ziegler T. Eckhardt E. Neumann K. Birault V. Synthesis  1992,  1013 

<A NAME="RT04406SS-6A">6a</A> Bonar-Law RP. Davis AP. Dorgan BJ. Reetz MT. Wersing A. Tetrahedron Lett.  1990,  31:  6725 

<A NAME="RT04406SS-6B">6b</A> Bonar-Law RP. Davis AP. Dorgan BJ. Tetrahedron Lett.  1990,  31:  6721 

<A NAME="RT04406SS-7">7</A> Djuric S. Venit J. Magnus P. Tetrahedron Lett.  1981,  22:  1787 

<A NAME="RT04406SS-8">8</A> Corey EJ. Hopkins PB. Tetrahedron Lett.  1982,  23:  4871 

<A NAME="RT04406SS-9A">9a</A> Cragg RH. Lane RD. J. Organomet. Chem.  1981,  212:  301 

<A NAME="RT04406SS-9B">9b</A> Lukasiak J. Radecki A. Lamparczyk H. Rocz. Chem.  1974,  48:  891 

<A NAME="RT04406SS-10A">10a</A> Markiewicz WT. Wiewiorowski M. Nucleic Acids Res., Spec. Publ.  1978,  4:  185 

<A NAME="RT04406SS-10B">10b</A> Markiewicz WT. J. Chem. Res., Miniprint  1979,  182 ; J. Chem. Res., Synop.; 1979, 24

<A NAME="RT04406SS-11">11</A> Pawlenko S. Organosilicon Chemistry   Walter de Gruyter Verlag; Berlin: 1986. 

<A NAME="RT04406SS-12A">12a</A> Tacke R. Linow H. Bio-organosilicon Chemistry, In The Chemistry of Organic Silicon Compounds   Vol. 1:  Patai S. Rappoport Z. Wiley; Chichester: 1998.  Chap. 19. p.1143 

<A NAME="RT04406SS-12B">12b</A> Tacke R. Wagner SA. Bio-organosilicon Chemistry, In The Chemistry of Organic Silicon Compounds   Vol. 2:  Rappoport Z. Apeloig Y. Wiley; Chichester: 1998.  Chap. 41. p.2363 

<A NAME="RT04406SS-13">13</A> Skydstrup T. Science of Synthesis   Vol. 4:  Fleming I. Thieme; Stuttgart: 2001.  p.269-291  

<A NAME="RT04406SS-14">14</A> Brook MA. Gottardo C. Balduzzi S. Mohamed M. Tetrahedron Lett.  1997,  38:  6997 ; and papers cited therein.

<A NAME="RT04406SS-15A">15a</A> Hwu JR. Wang N. Chem. Rev.  1989,  89:  1599 

<A NAME="RT04406SS-15B">15b</A> Hwu JR. Tsay SC. Cheng B.-L. Steric Effects of Silyl Groups, In The Chemistry of Organic Silicon Compounds   Vol. 2:  Rappoport Z. Apeloig Y. Wiley; New York: 1998.  Chap. 8. p.431 

<A NAME="RT04406SS-16">16</A> Nelson TD. Crouch RD. Synthesis  1996,  1031 

<A NAME="RT04406SS-17">17</A>

Silicon-Based Blocking Agents, In Supplement to the Gelest-Catalog (ABCR) Silicon, Germanium & Tin Compounds, Metal Alkoxides and Metal Diketonates; Larson, G. L.; see www.gelest.com.

<A NAME="RT04406SS-18">18</A> Verdegaal CHM. Jansse PL. de Rooij JFM. van Boom JH. Tetrahedron Lett.  1980,  1571 

<A NAME="RT04406SS-19">19</A> Oltvoort JJ. Kloosterman M. van Boom JH. Recl. Trav. Chim. Pay-Bas  1983,  102:  501 

<A NAME="RT04406SS-20">20</A> Kosma P. Schulz H. Brade H. Carbohydr. Res.  1989,  190:  191 

<A NAME="RT04406SS-21">21</A> Ziegler T. Eckhardt E. Pantkowski G. J. Carbohydr. Chem.  1994,  13:  81 

<A NAME="RT04406SS-22">22</A> Lindhorst TK. Essentials of Carbohydrate Chemistry and Biochemistry   2nd ed.:  Wiley-VCH; Weinheim: 2003.  p.67-68  

<A NAME="RT04406SS-23">23</A> Watanabe Y. Mitani M. Morita T. Ozaki S. J. Chem. Soc., Chem. Commun.  1989,  482 

<A NAME="RT04406SS-24">24</A> Krempner C. Jäger-Fiedler U. Mamat C. Spannenberg A. Weichert K. New J. Chem.  2005,  29:  1581 

<A NAME="RT04406SS-25">25</A> Westerhausen M. Schwarz W. Z. Anorg. Allg. Chem.  1993,  619:  1053 

<A NAME="RT04406SS-26">26</A>

Because of the low solubility of unprotected d-glucose and d-fructose in dichloromethane, silylations could not be carried out with these parent compounds.

<A NAME="RT04406SS-27">27</A> Brook MA. Gottardo C. Balduzzi S. Mohamed M. Tetrahedron Lett.  1997,  38:  6997 

<A NAME="RT04406SS-28A">28a</A> Brook MA. Balduzzi S. Mohamed M. Gottardo C. Tetrahedron  1999,  55:  10027 

<A NAME="RT04406SS-28B">28b</A> Balduzzi S. Brook MA. Tetrahedron  2000,  56:  1617 

<A NAME="RT04406SS-29">29</A> Herzog U. Roewer G. J. Organomet. Chem.  1997,  544:  217 

<A NAME="RT04406SS-30">30</A> Voitenko AD. Feldman DP. Schimanskaya AV. Lidak MYu. Khim. Pharm. Zh.  1983,  1:  82 

<A NAME="RT04406SS-31">31</A> Lichtenthaler FW. Hahn S. Flath F.-J. Liebigs Ann.  1995,  2081 

<A NAME="RT04406SS-32">32</A>

Sheldrick, G. M. SHELXS-97 and SHELXL-97, Programs for the Solution and Refinement of Crystal Structures; University of Göttingen, Germany, 1997.