Synthesis of daunosamine hydrochloride and intermediates used in its preparation
AssigneePurdue University
InventorRoy L. Whistler
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Abstract
A process for synthesizing daunosamine hydrochloride is disclosed. Intermediates useful for synthesizing daunosamine hydrochloride, and processes for preparing such intermediates, are also disclosed.
Claims20
A process for making alkyl L-daunosaminides comprising:
- a. oxidizing either L-fucal or 6-deoxy-L-idal;
- b. reacting the resultant 1,5-anhydro-3-oxo-2,3,6-trideoxy-L-threo-hex-1-enitol with a blocking agent to produce a compound having the formula ##STR31## wherein R is a blocking group;
- c. subjecting the resultant compound to alkyloxymercuration to produce a ketose having the formula ##STR32## wherein R.sup.1 is C.sub.1 -C.sub.6 alkyl;
- d. subjecting the resultant ketose to oximation to produce an oxime having the formula ##STR33## e. demercurating the oxime to a compound having the formula ##STR34## and f. reducing the resultant compound with simultaneous removal of the blocking group to produce alkyl L-daunosaminides.
A process for producing 1,5-anhydro-3-oxo-2,3,6-trideoxy-L-threo-hex-1-enitol comprising oxidizing L-fucal or 6-deoxy-L-idal.
A process for producing 1,5-anhydro-3-oxo-4-O-acetyl-2,3,6-trideoxy-L-threo-hex-1-enitol comprising acetylating 1,5-anhydro-3-oxo-2,3,6-trideoxy-L-threo-hex-1-enitol.
A process for producing methyl 2-chloromercuri-3-oxo-4-O-acetyl-2,3,6-trideoxy-L-(xylo,lyxo)-hexopyranosi de comprising subjecting 1,5-anhydro-3-oxo-4-O-acetyl-2,3,6-trideoxy-L-threo-hex-1-enitol to methoxymercuration.
A process for producing methyl 2-chloromercuri-3-oximino-4-O-acetyl-2,3,6-trideoxy-L-(xylo,lyxo)-hexopyra noside comprising subjecting methyl 2-chloromercuri-3-oxo-4-O-acetyl-2,3,6-trideoxy-L-(xylo,lyxo)-hexopyranosi de to oximation.
A process for producing methyl 3-oximino-4-O-acetyl-2,3,6-trideoxy-L-threo-hexopyranoside comprising demercurating methyl 2-chloromercuri-3-oximino-4-O-acetyl-2,3,6-trideoxy-L-(xylo,lyxo)-hexopyra noside.
A process for producing methyl 3-acetyloximino-4-O-acetyl-2,3,6-trideoxy-L-threo-hexopyranoside comprising acetylating methyl 3-oximino-4-O-acetyl-2,3,6-trideoxy-L-threo-hexopyranoside.
A process for producing methyl L-daunosaminide comprising reducing methyl 3-acetyloximino-4-O-acetyl-2,3,6-trideoxy-L-threo-hexopyranoside with simultaneous deacetylation.
A compound having the formula ##STR36## wherein R.sup.2 is ##STR37## or H.
A compound having the formula ##STR39## wherein R.sup.1 is C.sub.1 -C.sub.6 alkyl
- R is ##STR40## R.sup.3 is O.dbd., HON.dbd., ##STR41## R.sup.4 is HgCl or H provided that when R.sup.4 is HgCl, R.sup.3 must be O.dbd. or HON.dbd.;
- when R.sup.4 is H, R.sup.3 cannot be O.dbd..
Dependencies are inferred from the claim text.