Patent US4105696A successfully refreshed from Google Patents.
US4105696A
Expired / Lapsed
US
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Asymmetric synthesis of organic compounds
Assignee: Hoffmann La Roche Inc
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Filing: 1976-09-07
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Granted: 1978-08-08
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Expires: 1996-09-07
Abstract
Abstract Optically active organic compounds are prepared starting from optically inactive reactants by means of an optically active agent which influences the course of the reaction. In particular optically active compounds having a "meso" type carbon atom undergo an intramolecular ring closure in the presence of an optically active agent to yield an optically active product having one additional ring. The present process is particularly useful in the preparation of optically active bicyclic diketones which are important intermediates in the total synthesis of steroids.
Inventors
- 👤 Zoltan G. Hajos
- 👤 David R. Parrish
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-26 17:52
CPC Classifications
C; C07; C07D; C07D263/00; C07D263/52; C07C; C07C45/00; C07C45/56; C07C45/61; C07C45/65; C07C45/66; C07C45/67; C07C45/68; C07C45/69; C07C45/72; C07C45/73; C07C49/00; C07C49/587; C07C49/753; C07J; C07J15/00; C07C2603/00; C07C2603/02; C07C2603/04; C07C2603/06; C07C2603/10; C07C2603/12; C07C2603/16
Claims Analysis
Total Claims: 29
Claim 1
Independent Claim
155 words
The process for the preparation of optically active compounds utilizing as the starting material as optically inactive compound of the formula ##STR21## where R 1 is lower alkyl, aryl, aralkyl, lower alkenyl, lower alkynyl; R 2 is hydrogen, lower alkyl, aryl, aralkyl and --CH 2 ) p R 3 where p is an integer between 0 and 2 inclusive and R 3 is ##STR22## where R 4 is hydrogen or lower alkyl and R 5 is lower alkylenedioxy or arylenedioxy; n is an integer between 1 and 5 inclusive and m is an integer between 1 and 4 inclusive which process comprises cyclizing said optically inactive compound in the presence of an optically active α- or β-aminoalcohol or α- or β aminoacid to produce an optically active compound as product of the formula ##STR23## where R 1 , R 2 , m and n are as above having one more ring than said starting material.
Claim 2
Dependent Claim
155 words
The process for the preparation of optically active compounds utilizing as the starting material as optically inactive compound of the formula ##STR21## where R 1 is lower alkyl, aryl, aralkyl, lower alkenyl, lower alkynyl; R 2 is hydrogen, lower alkyl, aryl, aralkyl and --CH 2 ) p R 3 where p is an integer between 0 and 2 inclusive and R 3 is ##STR22## where R 4 is hydrogen or lower alkyl and R 5 is lower alkylenedioxy or arylenedioxy; n is an integer between 1 and 5 inclusive and m is an integer between 1 and 4 inclusive which process comprises cyclizing said optically inactive compound in the presence of an optically active α- or β-aminoalcohol or α- or β aminoacid to produce an optically active compound as product of the formula ##STR23## where R 1 , R 2 , m and n are as above having one more ring than said starting material.
Claim 3
Dependent Claim
24 words
The process of claim 1 wherein R 1 is lower alkyl, R 2 is hydrogen, m is 2 and n is 2 or 3.
Claim 4
Dependent Claim
22 words
The process of claim 1 wherein R 1 and R 2 are each lower alkyl, m is 2 and n is 2.
Claim 5
Dependent Claim
22 words
The process of claim 1 wherein R 1 is lower alkyl, R 2 is aralkyl, m is 2 and n is 2.
Claim 6
Dependent Claim
12 words
The process of claim 1 where said optically active α-aminoalcohol is (-)-ephedrine.
Claim 7
Dependent Claim
12 words
The process of claim 1 wherein said optically active α-aminoalcohol is (2S)-(+)-2-hydroxymethylpyrrolidine.
Claim 8
Dependent Claim
12 words
The process of claim 1 wherein said optically active α-aminoacid is (S)-(-)-proline.
Claim 9
Dependent Claim
12 words
The process of claim 1 wherein said optically active α-aminoacid is R-(+)-proline.
Claim 10
Dependent Claim
12 words
The process of claim 2 wherein said optically active α-aminoacid is S-(-)-trans-4-hydroxyproline.
Claim 11
Dependent Claim
12 words
The process of claim 1 wherein said optically active α-aminoacid is S-(-)-phenylalanine.
Claim 12
Dependent Claim
12 words
The process of claim 1 wherein said optically active is L-acetidine-2-carboxylic acid.
Claim 13
Dependent Claim
23 words
The process of claim 1 wherein a protic solvent medium is employed and said optically active compound obtained is primarily of formula III.
Claim 14
Dependent Claim
14 words
The process of claim 12 wherein said protic solvent medium comprises a lower alkanol.
Claim 15
Dependent Claim
12 words
The process of claim 13 wherein said protic solvent medium comprises 2-propanol.
Claim 16
Dependent Claim
22 words
The process of claim 1 wherein a nonprotic solvent medium is employed and said optically active compound is primarily of formula II.
Claim 17
Dependent Claim
12 words
The process of claim 15 wherein said non-protic solvent medium comprises acetonitrile.
Claim 18
Dependent Claim
12 words
The process of claim 15 wherein said non-protic solvent medium comprises N,N-dimethylformamide.
Claim 19
Dependent Claim
12 words
The process of claim 15 wherein said non-protic solvent medium comprises nitromethane.
Claim 20
Dependent Claim
40 words
A process for the preparation of optically active compounds of the formulae ##STR24## which process comprises cyclizing an optically inactive compound of the formula ##STR25## in the presence of an optically active α- or β-aminoacid or α- or -β aminoalcohol.
Claim 21
Dependent Claim
40 words
A process for the preparation of optically active compounds of the formulae ##STR24## which process comprises cyclizing an optically inactive compound of the formula ##STR25## in the presence of an optically active α- or β-aminoacid or α- or -β aminoalcohol.
Claim 22
Dependent Claim
14 words
The process of claim 19 wherein said optically active compounds are the dextrorotatory enantiomers.
Claim 23
Dependent Claim
12 words
The process of claim 19 wherein said optically active agent is S-(-)-proline.
Claim 24
Dependent Claim
37 words
Compounds of the formula ##STR26## where R 1 is lower alkyl; R 2 is hydrogen or lower alkyl; n is an integer between 1 and 5 inclusive and m is an integer between 1 and 4 inclusive.
Claim 25
Dependent Claim
37 words
Compounds of the formula ##STR26## where R 1 is lower alkyl; R 2 is hydrogen or lower alkyl; n is an integer between 1 and 5 inclusive and m is an integer between 1 and 4 inclusive.
Claim 26
Dependent Claim
8 words
The compound of claim 22 which is (+)-3a,4,7,7a-tetrahydro-3aβ-hydroxy-7aβ-methyl-1,5-(6H)-indandione.
Claim 27
Dependent Claim
8 words
The compound of claim 22 which is (-)-3a,4,7,7a-tetrahydro-3aβ-hydroxy-7aβ-methyl-1,5(6H)-indandione.
Claim 28
Dependent Claim
8 words
The compound of claim 22 which is (+)-7aβ-ethyl-3a,4,7,7a-tetrahydro-3aβ-hydroxy-1,5(6H)-indandione.
Claim 29
Dependent Claim
8 words
The compound of claim 22 which is (+)-3a,4,7,7a-tetrahydro-3aβ-hydroxy-4a,7aβ-dimethyl-1,5(6H)-indandione.
References Cited (Backward Citations)
US2542223A
Cited
US3682970A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-08-07 | 1982-02-06 | 1982-08-08 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-08-07 | 1986-02-06 | 1986-08-08 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-08-07 | 1990-02-06 | 1990-08-08 | $7700.00 | Window Closed / Lapsed |