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Synlett 2001; 2001(1): 0082-0086
DOI: 10.1055/s-2001-9699
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Synthesis of a (2R,6R)-2-(Hydroxymethyl)-6-propa-1,2-dienyl-2H-pyran-3(6H)-one Derivative, a New Enone for the Convergent Construction of C-Glycosides of C-Disaccharides

Yao-Hua Zhu* , Pierre Vogel
  • *Section de Chimie de l'Université, BCH, CH-1015 Lausanne-Dorigny, Switzerland; Fax +41 21 692 39 75; E-mail: pierre.vogel@ico.unil.ch
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Publication Date:
31 December 2001 (online)

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The previously unknown (2R,6R)-2[(tert-butyl)diphenylsilyloxy]-6-propa-1,2-dienyl-2H-pyran-3(6H)-one (16) was derived from tri-O-acetylglucal. Conjugate addition of PhSAlMe2 to 16 followed by enolate trapping with 1,2-O-isopropylidene-3-O-methyl-α-d-xylo-pentodialdo-1,4-furanose and NaBH4 reduction of the intermediate aldol furnished a new C-glycoside of a C-disaccharide: 4,8-anhydro-9-O-[(tert-butyl)diphenylsilyl]-6-[(5R)-1,2-O-isopropylidene-3-O-methyl-α-d-xylo-furanos-5-C-yl]-5-S-phenyl-1,2,3,6-tetradeoxy-5-thio-d-glycero-l-gulo-nona-1,2-dienitol (24). Similarly, conjugate addition of PhMe2SiZnMe2Li to 16, followed by cross-aldol reaction with 2,6-anhydro-1,3,4,5-tetra-O-[(tert-butyl)dimethylsilyl]-d-glycero-l-manno-heptose (27), and reduction gave either 4,8-anhydro-6-{(1S)-2,6-anhydro-3,4,5,7-tetra-O-[(tert-butyl)dimethylsilyl]-d-glycero-l-manno-heptitol-1-C-yl}-9-O-[tert-butyl)diphenylsilyl]-1,2,3,5,6-pentadeoxy-5-phenyldimethylsilyl-d-glycero-d-manno-(29) or l-gulo-nona-1,2-dienitol (30).

aldol reaction - carbohydrate-derived enone - conjugate addition - C-disaccharides - C-glycosides - glycal - C-silyl substituted carbohydrate