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Ring‐Closing Olefin Metathesis of 3,3′‐( D ‐Glycopyranosylidene)bis(1‐propene) Compounds as a Route to Anomeric Spiro Sugars
Author(s) -
Chen GuoRong,
Fei Zhong Bo,
Huang XiaoTing,
Xie YuYuan,
Xu JinLou,
Gola Joëlle,
Steng Michaela,
Praly JeanPierre
Publication year - 2001
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/1099-0690(200108)2001:15<2939::aid-ejoc2939>3.0.co;2-h
Subject(s) - chemistry , anomer , propene , yield (engineering) , ring closing metathesis , olefin fiber , metathesis , salt metathesis reaction , catalysis , olefin metathesis , ring (chemistry) , organic chemistry , medicinal chemistry , polymerization , materials science , polymer , metallurgy
New peracetylated 3,3′‐( D ‐glycopyranosylidene)bis(1‐propene), prepared from peracetylated anomeric sugar dihalides and allyltributyltin in excess under UV irradiation conditions (AIBN, ca. 35 °C), lent themselves to ring‐closing olefin metathesis in the presence of Grubbs’ catalyst (6 mol %) to afford the corresponding peracetylated spiro[1,5‐anhydro‐ D ‐glycopyranositol‐1,4′‐cyclopent‐1′‐enes] ( D ‐ gluco : 81%, D ‐ manno : 89%, D ‐ galacto : 72% isolated yield), which could be deacetylated quantitatively. The bis(allylation) reaction ( D ‐ gluco : 40%, D ‐ manno : 34%, D ‐ galacto : 24% isolated yield) was in competition with radical‐induced rearrangement and elimination reactions. The last process, found to be favored at higher temperature (80 °C), opens an easy route to sugar dienes difficult to prepare otherwise.