合成路线:The partial demethylation of (?-podophyllotoxin (I) with HBr in ether - dichloromethane,followed by alkaline hydrolysis with BaCO3 in aqueous acetone,gives (?-4'-O-demethyl-1-epipodophyllotoxin (II),which is partially esterified with chloroacetyl chloride and pyridine,yielding (?-4'-O-chloroacetyl-4'-O-demethyl-1-epipodophyllotoxin (III).The glycosidation of (III) with 2-(benzyloxocarbonylamino)-3-O-chloroacetyl-2-deoxy-4,6-O-ethylidene-beta-D-glucopyranose (IV) by means of BF3 ethearate in dichloromethane affords (?-1-O-[2-(benzyloxycarbonylamino)-3-O-chloroacetyl-2-deoxy-4,6-O-ethylidene-beta-D-glucopyranosyl]-4'-O-(chloroacetyl)-4'-O-demethyl-1-epipodophyllotoxin (?-(V) which,after separation of the diastereomers and elimination of the protecting groups with zinc acetate in refluxing methanol and H2 over Pd/C in ethyl acetate - ethanol,gives 1-O-(2-amino-2-deoxy-4,6-O-ethylidene-beta-D-glucopyranosyl)-4'-O-demethyl-1-epipodophyllotoxin (VI).Finally,this compound is methylated with formaldehyde and sodium cyanoborohydride in methanol.The sugar moiety has been obtained as follows: The reaction of 2-(benzyloxycarbonylamino)-2-deoxy-beta-D-glucopyranose (VII) with acetaldehyde and concentrated H2SO4 gives 2-(benzyloxycarbonylamino)-2-deoxy-4,6-O-ethylidene-beta-D-glucopyranose (VIII),which is then esterified with chloroacetyl chloride to (IV).
参考文献标题:Studies on lignan lactone antitumor agents.II.Synthesis of N-alkylamino- and 2,6-dideoxy-2-aminoglycosidic lignan variants related to podophyllotoxin
文献作者:Saito,H.; Yoshikawa,H.; Nishimura,Y.; Kondo,S.; Takeuchi,T.; Umezawa,H.
参考来源:Chem Pharm Bull 1986,34(9),3741-46
合成路线:The partial demethylation of (?-podophyllotoxin (I) with HBr in ether - dichloromethane,followed by alkaline hydrolysis with BaCO3 in aqueous acetone,gives (?-4'-O-demethyl-1-epipodophyllotoxin (II),which is partially esterified with chloroacetyl chloride and pyridine,yielding (?-4'-O-chloroacetyl-4'-O-demethyl-1-epipodophyllotoxin (III).The glycosidation of (III) with 2-(benzyloxocarbonylamino)-3-O-chloroacetyl-2-deoxy-4,6-O-ethylidene-beta-D-glucopyranose (IV) by means of BF3 ethearate in dichloromethane affords (?-1-O-[2-(benzyloxycarbonylamino)-3-O-chloroacetyl-2-deoxy-4,6-O-ethylidene-beta-D-glucopyranosyl]-4'-O-(chloroacetyl)-4'-O-demethyl-1-epipodophyllotoxin (?-(V) which,after separation of the diastereomers and elimination of the protecting groups with zinc acetate in refluxing methanol and H2 over Pd/C in ethyl acetate - ethanol,gives 1-O-(2-amino-2-deoxy-4,6-O-ethylidene-beta-D-glucopyranosyl)-4'-O-demethyl-1-epipodophyllotoxin (VI).Finally,this compound is methylated with formaldehyde and sodium cyanoborohydride in methanol.The sugar moiety has been obtained as follows: The reaction of 2-(benzyloxycarbonylamino)-2-deoxy-beta-D-glucopyranose (VII) with acetaldehyde and concentrated H2SO4 gives 2-(benzyloxycarbonylamino)-2-deoxy-4,6-O-ethylidene-beta-D-glucopyranose (VIII),which is then esterified with chloroacetyl chloride to (IV).
参考文献标题:Syntheses of all four possible diastereomers of etoposide and its aminoglycosidic analogues via optical resolution of (?-podophyllotoxin by glucosidation with D- and L-sugars
文献作者:Saito,H.; Nishimura,Y.; Kondo,S.; Umezawa,H.
参考来源:Chem Lett 1987,5(5),799-802
合成路线:The partial demethylation of (?-podophyllotoxin (I) with HBr in ether - dichloromethane,followed by alkaline hydrolysis with BaCO3 in aqueous acetone,gives (?-4'-O-demethyl-1-epipodophyllotoxin (II),which is partially esterified with chloroacetyl chloride and pyridine,yielding (?-4'-O-chloroacetyl-4'-O-demethyl-1-epipodophyllotoxin (III).The glycosidation of (III) with 2-(benzyloxocarbonylamino)-3-O-chloroacetyl-2-deoxy-4,6-O-ethylidene-beta-D-glucopyranose (IV) by means of BF3 ethearate in dichloromethane affords (?-1-O-[2-(benzyloxycarbonylamino)-3-O-chloroacetyl-2-deoxy-4,6-O-ethylidene-beta-D-glucopyranosyl]-4'-O-(chloroacetyl)-4'-O-demethyl-1-epipodophyllotoxin (?-(V) which,after separation of the diastereomers and elimination of the protecting groups with zinc acetate in refluxing methanol and H2 over Pd/C in ethyl acetate - ethanol,gives 1-O-(2-amino-2-deoxy-4,6-O-ethylidene-beta-D-glucopyranosyl)-4'-O-demethyl-1-epipodophyllotoxin (VI).Finally,this compound is methylated with formaldehyde and sodium cyanoborohydride in methanol.The sugar moiety has been obtained as follows: The reaction of 2-(benzyloxycarbonylamino)-2-deoxy-beta-D-glucopyranose (VII) with acetaldehyde and concentrated H2SO4 gives 2-(benzyloxycarbonylamino)-2-deoxy-4,6-O-ethylidene-beta-D-glucopyranose (VIII),which is then esterified with chloroacetyl chloride to (IV).
参考文献标题:NK-611
文献作者:Prous,J.; Castar,J.
参考来源:Drugs Fut 1991,16(2),113
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