US4413120A
Expired / Lapsed
US
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Process for producing acosamine, daunosamine, 1-thioacosamine and related compounds
Assignee: Purdue Research Foundation
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Filing: 1981-04-06
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Granted: 1983-11-01
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Expires: 2001-04-06
Abstract
Abstract A process for synthesizing acosamine, daunosamine and 1-thioacosamines from L-rhamnal is disclosed that can generally be characterized by Michael addition of an alkoxide or thioalkoxide to the enone formed by allylic oxidation of L-rhamnal to directly generate the 2-deoxy functionality, and stereospecific reduction of the oxime to the arabino compound which establishes configuration at C-3 and generates a compound which requires only epirmerization at C-4 to yield the desired product. The synthesis of anthracycline antibiotics incorporating these sugars or their derivatives by glycosidation of the glycone is also disclosed.
Inventors
- 👤 Roy L. Whistler
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 16:19
CPC Classifications
C; C07; C07H; C07H15/00; C07H15/02; C07H15/14; C07H15/04
Claims Analysis
Total Claims: 9
Claim 1
Independent Claim
41 words
A process for producing a thiohexopyranoside which comprises reacting a hex-1-en-3-ulose with an alkylthiol or a salt thereof in the presence of a base so as to effect a Michael Addition of a thioalkyl group at the 1-position of said hex-1-en-3-ulose.
Claim 2
Dependent Claim
41 words
A process for producing a thiohexopyranoside which comprises reacting a hex-1-en-3-ulose with an alkylthiol or a salt thereof in the presence of a base so as to effect a Michael Addition of a thioalkyl group at the 1-position of said hex-1-en-3-ulose.
Claim 3
Dependent Claim
10 words
The process of claim 1 wherein said hex-1-en-3-ulose is 1,5-anhydro-2,6-dideoxy-α-L-erythro-hex-1-en-3-ulose.
Claim 4
Dependent Claim
30 words
The process of claim 2 wherein said alkyl thiol or salt thereof is selected from the group consisting of benzyl mercaptan, potassium thioacetate, and the potassium salt of benzyl mercaptan.
Claim 5
Dependent Claim
89 words
A process for producing L-thioacosamine derivatives which comprises: oxidizing L-rhamnal to produce 1,5 anhydro-2,6-dideoxy-α-L-erythro-hex-1-en-3-ulose, reacting said 1,5 anhydro-2,6-dideoxy-α-L-erythro-hex-1-en-3-ulose with an alkylthiol or salt thereof in the presence of a strong base to produce alkyl 2,6-dideoxy-1-thio-α-L-erythro-hexopyranosid-3-ulose by Michael addition, reacting said alkyl 2,6-dideoxy-1-thio-α-L-erythro-hexopyranosid-3-ulose with hydroxylamine to introduce an oximino group at the 3-position; reacting the resultant 3-oximino compound with acetic anhydride to produce the di-O-acetyl compound; ##STR3## and stereospecifically reducing said di-O-acetyl compound with borane in tetrahydrofuran to convert the 3-oximino group to a 3-amido group of the arabino configuration.
Claim 6
Dependent Claim
89 words
A process for producing L-thioacosamine derivatives which comprises: oxidizing L-rhamnal to produce 1,5 anhydro-2,6-dideoxy-α-L-erythro-hex-1-en-3-ulose, reacting said 1,5 anhydro-2,6-dideoxy-α-L-erythro-hex-1-en-3-ulose with an alkylthiol or salt thereof in the presence of a strong base to produce alkyl 2,6-dideoxy-1-thio-α-L-erythro-hexopyranosid-3-ulose by Michael addition, reacting said alkyl 2,6-dideoxy-1-thio-α-L-erythro-hexopyranosid-3-ulose with hydroxylamine to introduce an oximino group at the 3-position; reacting the resultant 3-oximino compound with acetic anhydride to produce the di-O-acetyl compound; ##STR3## and stereospecifically reducing said di-O-acetyl compound with borane in tetrahydrofuran to convert the 3-oximino group to a 3-amido group of the arabino configuration.
Claim 7
Dependent Claim
17 words
The process of claim 4 wherein said alkyl thiol is benzyl mercaptan and said base is pyridine.
Claim 8
Dependent Claim
78 words
A process for producing L-acosamine derivatives comprising: oxidizing L-rhamnal to produce 1,5-anhydro-2,6-dideoxy-α-L-erythro-hex-1-en-3-ulose; reacting 2,6-dideoxy-α-L-erythro-hex-1-en-3-ulose with sodium methoxide in methanol to produce the compound methyl 2,6-dideoxy-α-L-erythro-hexopyranosid-3-ulose, reacting the resultant methyl 2,6-dideoxy-α-L-erythro-hexopyranosid-3-ulose with hydroxylamine to introduce an oximino group at the 3-position, reacting the resultant 3-oximino compound with acetic anhydride to produce the di-O-acetyl compound ##STR4## and stereospecifically reducing the resultant di-O-acetyl compound with borane in tetrahydrofuran to convert the 3-oximino group to a 3-amido group of the arabino configuration.
Claim 9
Dependent Claim
78 words
A process for producing L-acosamine derivatives comprising: oxidizing L-rhamnal to produce 1,5-anhydro-2,6-dideoxy-α-L-erythro-hex-1-en-3-ulose; reacting 2,6-dideoxy-α-L-erythro-hex-1-en-3-ulose with sodium methoxide in methanol to produce the compound methyl 2,6-dideoxy-α-L-erythro-hexopyranosid-3-ulose, reacting the resultant methyl 2,6-dideoxy-α-L-erythro-hexopyranosid-3-ulose with hydroxylamine to introduce an oximino group at the 3-position, reacting the resultant 3-oximino compound with acetic anhydride to produce the di-O-acetyl compound ##STR4## and stereospecifically reducing the resultant di-O-acetyl compound with borane in tetrahydrofuran to convert the 3-oximino group to a 3-amido group of the arabino configuration.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-10-31 | 1987-05-02 | 1987-11-01 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-10-31 | 1991-05-02 | 1991-11-01 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-10-31 | 1995-05-02 | 1995-11-01 | $7700.00 | Window Closed / Lapsed |