IL43597A - Stereospecific preparation of chiral 2-alkoxycarbonylhexyl-4-hydroxy-2-cyclopenten-1-ones - Google Patents
Stereospecific preparation of chiral 2-alkoxycarbonylhexyl-4-hydroxy-2-cyclopenten-1-onesInfo
- Publication number
- IL43597A IL43597A IL43597A IL4359773A IL43597A IL 43597 A IL43597 A IL 43597A IL 43597 A IL43597 A IL 43597A IL 4359773 A IL4359773 A IL 4359773A IL 43597 A IL43597 A IL 43597A
- Authority
- IL
- Israel
- Prior art keywords
- dione
- accomplished
- ester
- enol
- enolization
- Prior art date
Links
- 230000000707 stereoselective effect Effects 0.000 title 1
- 238000000034 method Methods 0.000 claims 10
- -1 2-substituted-4 (R) - -hydroxy-2-cyclopenten-l-one Chemical class 0.000 claims 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 8
- 238000005837 enolization reaction Methods 0.000 claims 7
- 125000004432 carbon atom Chemical group C* 0.000 claims 4
- 150000002084 enol ethers Chemical class 0.000 claims 4
- 125000000217 alkyl group Chemical group 0.000 claims 3
- 150000001875 compounds Chemical class 0.000 claims 3
- 150000002148 esters Chemical class 0.000 claims 3
- 238000006722 reduction reaction Methods 0.000 claims 3
- VOYADQIFGGIKAT-UHFFFAOYSA-N 1,3-dibutyl-4-hydroxy-2,6-dioxopyrimidine-5-carboximidamide Chemical compound CCCCn1c(O)c(C(N)=N)c(=O)n(CCCC)c1=O VOYADQIFGGIKAT-UHFFFAOYSA-N 0.000 claims 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 2
- 125000003342 alkenyl group Chemical group 0.000 claims 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 2
- BUZZUHJODKQYTF-UHFFFAOYSA-N 1-iodo-3-methylbutane Chemical compound CC(C)CCI BUZZUHJODKQYTF-UHFFFAOYSA-N 0.000 claims 1
- JVSFQJZRHXAUGT-UHFFFAOYSA-N 2,2-dimethylpropanoyl chloride Chemical compound CC(C)(C)C(Cl)=O JVSFQJZRHXAUGT-UHFFFAOYSA-N 0.000 claims 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 230000006179 O-acylation Effects 0.000 claims 1
- 238000010934 O-alkylation reaction Methods 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims 1
- 239000012346 acetyl chloride Substances 0.000 claims 1
- 230000010933 acylation Effects 0.000 claims 1
- 238000005917 acylation reaction Methods 0.000 claims 1
- 230000029936 alkylation Effects 0.000 claims 1
- 238000005804 alkylation reaction Methods 0.000 claims 1
- 125000005228 aryl sulfonate group Chemical group 0.000 claims 1
- 235000010290 biphenyl Nutrition 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 125000004185 ester group Chemical group 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 239000011630 iodine Chemical group 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- FMKOJHQHASLBPH-UHFFFAOYSA-N isopropyl iodide Chemical compound CC(C)I FMKOJHQHASLBPH-UHFFFAOYSA-N 0.000 claims 1
- 239000003446 ligand Substances 0.000 claims 1
- 125000001624 naphthyl group Chemical group 0.000 claims 1
- 125000004430 oxygen atom Chemical group O* 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- 229910052703 rhodium Inorganic materials 0.000 claims 1
- 239000010948 rhodium Substances 0.000 claims 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/738—Esters of keto-carboxylic acids or aldehydo-carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C405/00—Compounds containing a five-membered ring having two side-chains in ortho position to each other, and having oxygen atoms directly attached to the ring in ortho position to one of the side-chains, one side-chain containing, not directly attached to the ring, a carbon atom having three bonds to hetero atoms with at the most one bond to halogen, and the other side-chain having oxygen atoms attached in gamma-position to the ring, e.g. prostaglandins ; Analogues or derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Claims (10)
1. A method for preparing 2-substituted-4 (R) - -hydroxy-2-cyclopenten-l-one of the formula where R is an alkyl radical containing 1 to 4 carbon atoms , characterized by: (a) asymmetrically reducing a compound of the formula where R has the same meaning as above, to obtain a corresponding 2-subs ituted- (R) -hydroxy -cyclopentane-1 , 3-dione of the formula where R has the same meaning as above; (b) subjecting the dione to enolization through selective O-acylation with compounds of the formulae 43597/3 -CO-X or R' -SO where X is I, CI, Br, 0-CO-R' or -OS02R' and R' is a group selected from unsub s tituted or. halogen-, alkyl- or alkoxy- subs tituted phenyl, benzyl, biphenyl or naphthyl groups, or > _ alkyl or alkenyl having up to 6 carbon atoms , or through selective O-alkylation under mild alkaline conditions with compounds of the formula R"X where R" is a group selected from alkyl or alkenyl having up to 6 carbon atoms, benzyl, diphenylmethyl or ester groups of the formula D i l l -CH2-COOR' ' ' or -CH-COOR1 ' * where R' 11 is a hydrocarbon radical containing from about 1 to 6 carbon atoms and X is chlorine, bromine, iodine or the alkyl -substituted or unsubstituted aryl sulfonate, sulfate or isocynate radical whereby acylation or alkylation of the oxygen atom at the C-l position of the dione is preferentially promoted, thereby to convert the dione to an enol ester or enol ether configuration, respectively, of the formula where R has the same meaning as above; 43597/2 (c) separating the desired substituted C-1 enol ester or ether from the substituted C-3 enol ester or ether; (d) reducing the separated C-1 substituted enol ester or ether; and (e) recovering the desired 2 -substituted-4(R) -hydroxy-2-cyclopenten-l-one from the reduction reaction mixture .
2. The method of Claim 1 wherein the 2 -substituent on the trione is the 61 -carbomethoxyhexy 1 group and 2 - (6 ' -carbomethoxyhexyl) - 4 (R) -hydroxy - 2 -eye lopenten-1- one is recovered as the desired product.
3. The method of Claim 1 or 2 wherein the reduction of the trione is accomplished by catalytic hydrogenation in the presence of a complex of rhodium with a chiral phosphine ligand.
4. The method of Claim 1 or 2 wherein enolization to the enol ester configuration is accomplished by reacting the dione with pivaloyl chloride.
5. The method of Claim 1 or 2 wherein enolization to the enol ether configuration is accomplished by reacting the dione with isoamyl iodide.
6. The method of Claim 1 or 2 wherein enolization to the enol ether configuration is accomplished by reacting the dione with isopropyl iodide.
7. The method of Claim 1 or 2 wherein enolization to the mono-enolbenzoate ester configuration is accomplished by reacting the dione with one molar equivalent of benzoyl chloride .
8. The method of Claim 1 or 2 wherein enolization to the di-enolbenzoate ester configuration is accomplished by reacting the dione with two molar equivalents of benzoyl chloride.
9. The method of Claim 1 or 2 wherein enolization to the enol ester configuration is accomplished by reacting the dione with acetyl chloride.
10. The method of Claim 1 or 2 wherein the reduction of the enol ester or enol ether is accomplished by reacting the said ester or ether with sodium dihydro-bis
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US30976672A | 1972-11-27 | 1972-11-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IL43597A0 IL43597A0 (en) | 1974-03-14 |
| IL43597A true IL43597A (en) | 1976-09-30 |
Family
ID=23199601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL43597A IL43597A (en) | 1972-11-27 | 1973-11-08 | Stereospecific preparation of chiral 2-alkoxycarbonylhexyl-4-hydroxy-2-cyclopenten-1-ones |
Country Status (25)
| Country | Link |
|---|---|
| JP (1) | JPS5328908B2 (en) |
| AR (1) | AR198543A1 (en) |
| AT (1) | AT330143B (en) |
| AU (1) | AU459800B2 (en) |
| BE (1) | BE807825A (en) |
| BG (1) | BG21204A3 (en) |
| CA (1) | CA1034139A (en) |
| CH (1) | CH599098A5 (en) |
| CS (1) | CS170480B2 (en) |
| DD (1) | DD108516A5 (en) |
| DE (1) | DE2358781C3 (en) |
| ES (1) | ES420855A1 (en) |
| FR (1) | FR2207905B1 (en) |
| GB (1) | GB1440108A (en) |
| HU (1) | HU169638B (en) |
| IE (1) | IE38497B1 (en) |
| IL (1) | IL43597A (en) |
| NL (1) | NL7316147A (en) |
| NO (1) | NO138905C (en) |
| PH (1) | PH10276A (en) |
| PL (1) | PL91162B1 (en) |
| RO (1) | RO63011A (en) |
| SE (1) | SE406462B (en) |
| SU (1) | SU617005A3 (en) |
| ZA (1) | ZA738581B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU529883B2 (en) * | 1978-09-04 | 1983-06-23 | Australian National University, The | Substituted cyclopentenones |
| JPS56159683U (en) * | 1980-04-28 | 1981-11-28 | ||
| US5254708A (en) * | 1987-06-16 | 1993-10-19 | Nissan Chemical Industries, Ltd. | Substituted cyclic ketones, substituted cyclic enones, and process for producing the same |
| US5231208A (en) * | 1987-06-16 | 1993-07-27 | Nissan Chemical Industries, Ltd. | Substituted cyclic ketones, substituted cyclic enones, and process for producing the same |
| US5227505A (en) * | 1987-06-16 | 1993-07-13 | Nissan Chemical Industries, Ltd. | Substituted cyclic ketones, substituted cyclic enones, and process for producing the same |
| JP2696933B2 (en) * | 1987-06-16 | 1998-01-14 | 日産化学工業株式会社 | Substituted cyclic ketones and substituted cyclic enones and methods for their preparation |
-
1973
- 1973-11-07 CA CA185,210A patent/CA1034139A/en not_active Expired
- 1973-11-07 IE IE2003/73A patent/IE38497B1/en unknown
- 1973-11-08 IL IL43597A patent/IL43597A/en unknown
- 1973-11-08 ZA ZA738581A patent/ZA738581B/en unknown
- 1973-11-08 AU AU62283/73A patent/AU459800B2/en not_active Expired
- 1973-11-09 GB GB5222073A patent/GB1440108A/en not_active Expired
- 1973-11-15 PH PH15227A patent/PH10276A/en unknown
- 1973-11-16 AR AR251028A patent/AR198543A1/en active
- 1973-11-20 CH CH1628373A patent/CH599098A5/xx not_active IP Right Cessation
- 1973-11-22 JP JP13086973A patent/JPS5328908B2/ja not_active Expired
- 1973-11-22 AT AT980073A patent/AT330143B/en not_active IP Right Cessation
- 1973-11-26 RO RO7300076778A patent/RO63011A/en unknown
- 1973-11-26 SU SU731975423A patent/SU617005A3/en active
- 1973-11-26 BG BG25076A patent/BG21204A3/xx unknown
- 1973-11-26 FR FR7341997A patent/FR2207905B1/fr not_active Expired
- 1973-11-26 PL PL1973166812A patent/PL91162B1/en unknown
- 1973-11-26 BE BE138190A patent/BE807825A/en not_active IP Right Cessation
- 1973-11-26 NL NL7316147A patent/NL7316147A/xx unknown
- 1973-11-26 ES ES420855A patent/ES420855A1/en not_active Expired
- 1973-11-26 HU HUWI246A patent/HU169638B/hu unknown
- 1973-11-26 CS CS8114A patent/CS170480B2/cs unknown
- 1973-11-26 NO NO734495A patent/NO138905C/en unknown
- 1973-11-26 DE DE2358781A patent/DE2358781C3/en not_active Expired
- 1973-11-26 DD DD174893A patent/DD108516A5/en unknown
- 1973-11-26 SE SE737315982A patent/SE406462B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| RO63011A (en) | 1978-05-15 |
| SE406462B (en) | 1979-02-12 |
| DD108516A5 (en) | 1974-09-20 |
| JPS4982649A (en) | 1974-08-08 |
| ES420855A1 (en) | 1976-04-01 |
| DE2358781C3 (en) | 1979-11-08 |
| IL43597A0 (en) | 1974-03-14 |
| CS170480B2 (en) | 1976-08-27 |
| BG21204A3 (en) | 1976-03-20 |
| FR2207905A1 (en) | 1974-06-21 |
| CH599098A5 (en) | 1978-05-12 |
| DE2358781B2 (en) | 1979-01-25 |
| HU169638B (en) | 1976-12-28 |
| GB1440108A (en) | 1976-06-23 |
| IE38497L (en) | 1974-05-27 |
| ZA738581B (en) | 1974-09-25 |
| AR198543A1 (en) | 1974-06-28 |
| ATA980073A (en) | 1975-09-15 |
| PH10276A (en) | 1976-11-03 |
| NO138905C (en) | 1978-12-06 |
| IE38497B1 (en) | 1978-03-29 |
| AU459800B2 (en) | 1975-04-10 |
| JPS5328908B2 (en) | 1978-08-17 |
| AT330143B (en) | 1976-06-10 |
| SU617005A3 (en) | 1978-07-25 |
| CA1034139A (en) | 1978-07-04 |
| NL7316147A (en) | 1974-05-29 |
| PL91162B1 (en) | 1977-02-28 |
| DE2358781A1 (en) | 1974-06-12 |
| FR2207905B1 (en) | 1978-02-24 |
| BE807825A (en) | 1974-03-15 |
| NO138905B (en) | 1978-08-28 |
| AU6228373A (en) | 1975-04-10 |
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