ABSTRACT
The magnitude of the one-bond coupling constant between C(1) and H(1) in 2,3-anhydro-O-furanosides has been shown to be sensitive to the stereochemistry at the anomeric center. A panel of 24 compounds was studied and in cases where the anomeric hydrogen is trans to the epoxide moiety, (1)J[C(1)-H(1)] = 163-168 Hz; and when this hydrogen is cis to the oxirane ring, ((1)J[C(1)-H(1)] = 171-174 Hz. In contrast, for 2,3-anhydro-S-glycosides, the size of the (1)J[C(1)-H(1)] is not sensitive to C(1) stereochemistry. Computational studies on all four methyl 2,3-anhydro-O-furanosides (5-8) demonstrated that (1)J[C(1)-H(1)] was inversely proportional to the length of the C(1)-H(1) bond. A previously reported equation, which relates C(1)-H(1) bond distance and atomic charges to (1)J[C(1)-H(1)] magnitudes, could be used to accurately predict the J values in the alpha-lyxo (5) and beta-ribo (8) isomers. In contrast, with the beta-lyxo (6) and alpha-ribo isomers (7), this equation underestimated the size of these coupling constants by 10-20 Hz.
Subject(s)
Furans/chemical synthesis , Monosaccharides , Monosaccharides/chemical synthesis , Thioglycosides/chemical synthesis , Furans/chemistry , Molecular Conformation , Monosaccharides/chemistry , Statistics as Topic , Thioglycosides/chemistryABSTRACT
[reaction: see text] The stereocontrolled synthesis of 2,3-anhydro-beta-D-lyxofuranosyl glycosides from thioglycoside 2 and glycosyl sulfoxide 3 is reported.
Subject(s)
Glycosides/chemical synthesis , Glycosides/chemistry , Glycosylation , Molecular Structure , Stereoisomerism , Thioglycosides/chemistryABSTRACT
An efficient synthesis of methyl 2,3-anhydro-alpha-D-ribofuranoside is reported. Its preparation is achieved via a four-step sequence from methyl 2,3,5-tri-O-benzoyl-alpha-D-arabinofuranoside in 74% overall yield.
Subject(s)
Anhydrides/chemical synthesis , Glycosides/chemical synthesis , Ribose/chemical synthesis , Anhydrides/chemistry , Glycosides/chemistry , Ribose/analogs & derivatives , Ribose/chemistry , StereoisomerismABSTRACT
Synthesis and antitumor activity of goniofufurone analogues 15, 16, 17, 33, and 46 is reported. Key step in the synthesis is Pd (II) mediated oxidative cyclisation of vinyl-(hydroxy) furans 18, 19 to the corresponding lactols 32, 43. Cytotoxicities of 15, 16, 17, 33, and 46 tested against six human cancer cell lines are reported. Change of stereochemistry at C-5, C-6 and C-7 position of goniofufurone (1) did not enhance the cytotoxicities significantly.
