CS201352B1 - Process for preparing 2,3 -0-isopropyliden-2,3-dihydroxy-1,4-bis/diphenylphosphine/butane - Google Patents
Process for preparing 2,3 -0-isopropyliden-2,3-dihydroxy-1,4-bis/diphenylphosphine/butane Download PDFInfo
- Publication number
- CS201352B1 CS201352B1 CS786684A CS668478A CS201352B1 CS 201352 B1 CS201352 B1 CS 201352B1 CS 786684 A CS786684 A CS 786684A CS 668478 A CS668478 A CS 668478A CS 201352 B1 CS201352 B1 CS 201352B1
- Authority
- CS
- Czechoslovakia
- Prior art keywords
- dihydroxy
- butane
- bis
- diphenylphosphine
- isopropyliden
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000001273 butane Substances 0.000 title 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 title 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 title 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 title 1
- 238000002360 preparation method Methods 0.000 claims description 4
- ILCLANVYOPHXJF-UHFFFAOYSA-N diphenylphosphane;sodium Chemical compound [Na].C=1C=CC=CC=1PC1=CC=CC=C1 ILCLANVYOPHXJF-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 4
- 150000001371 alpha-amino acids Chemical class 0.000 description 4
- 235000008206 alpha-amino acids Nutrition 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical class PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- VCHDBLPQYJAQSQ-KYJUHHDHSA-N [(4r,5r)-5-(diphenylphosphanylmethyl)-2,2-dimethyl-1,3-dioxolan-4-yl]methyl-diphenylphosphane Chemical compound C([C@@H]1OC(O[C@H]1CP(C=1C=CC=CC=1)C=1C=CC=CC=1)(C)C)P(C=1C=CC=CC=1)C1=CC=CC=C1 VCHDBLPQYJAQSQ-KYJUHHDHSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- UAEUEBGUIQLDPG-VDTYLAMSSA-N (2r,3s)-5-methylhex-4-ene-1,2,3,4-tetrol Chemical compound CC(C)=C(O)[C@@H](O)[C@H](O)CO UAEUEBGUIQLDPG-VDTYLAMSSA-N 0.000 description 1
- XODAOBAZOQSFDS-UHFFFAOYSA-N 2-acetamido-3-phenylprop-2-enoic acid Chemical compound CC(=O)NC(C(O)=O)=CC1=CC=CC=C1 XODAOBAZOQSFDS-UHFFFAOYSA-N 0.000 description 1
- FWXAUDSWDBGCMN-UHFFFAOYSA-N 3-diphenylphosphanylbutan-2-yl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)C(C)C(C)P(C=1C=CC=CC=1)C1=CC=CC=C1 FWXAUDSWDBGCMN-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 150000007649 L alpha amino acids Chemical class 0.000 description 1
- 239000001358 L(+)-tartaric acid Substances 0.000 description 1
- 235000011002 L(+)-tartaric acid Nutrition 0.000 description 1
- FEWJPZIEWOKRBE-LWMBPPNESA-N L-(+)-Tartaric acid Natural products OC(=O)[C@@H](O)[C@H](O)C(O)=O FEWJPZIEWOKRBE-LWMBPPNESA-N 0.000 description 1
- 150000008575 L-amino acids Chemical class 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- FNIATMYXUPOJRW-UHFFFAOYSA-N cyclohexylidene Chemical group [C]1CCCCC1 FNIATMYXUPOJRW-UHFFFAOYSA-N 0.000 description 1
- PWAPCRSSMCLZHG-UHFFFAOYSA-N cyclopentylidene Chemical group [C]1CCCC1 PWAPCRSSMCLZHG-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000009905 homogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- AUONNNVJUCSETH-UHFFFAOYSA-N icosanoyl icosanoate Chemical compound CCCCCCCCCCCCCCCCCCCC(=O)OC(=O)CCCCCCCCCCCCCCCCCCC AUONNNVJUCSETH-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Vynález se týká způsobu přípravy 2,3-0ispopr:opyliden-2,3-dihyd'roxy-l,4,bis(difenylfosfino)butanu, jako katalyzátoru potřebného k asymetrické hydrogenaci acetylderivátů a, (3-nenasycených α-aminokyselin na L — a — aminokyseliny.BACKGROUND OF THE INVENTION The present invention relates to a process for the preparation of 2,3-di-propylidyl-2,3-dihydroxy-1,4, bis (diphenylphosphino) butane as a catalyst required for the asymmetric hydrogenation of acetylderivatives of α, (3-unsaturated α-amino acids to L - and amino acids.
α, β — nenasycené α-aminokyseliny jsou prekursory důležitých α-aminokyselin a jejich hydrogenace má v současné době díky aktualitě výroby L-aminokyselín značný význam.α, β - unsaturated α-amino acids are precursors of important α-amino acids and their hydrogenation is currently of great importance due to the latest production of L-amino acids.
Je známo, že se asymetrická homogenní /hydnogenace úspěšně provádí v přítomnosti komplexů přechodných kovů 8. skupiny, které obsahují ve své koordinační sféře chirální ligand. Nejvyšších optických výtěžků bylo dosaženo pomocí komplexů s chirálním difosfinem, připravených in šitu z olefinického komplexu, rhodia typu R-h(en)2Cl2 a 2,3-0-isopropyliden- (nebo cyklohexyliden- či cyklopentyliden)-2,3-dihydroxy-1,4-bis(dif enylfosfino) butanu. Tento difosfin je znám pod názvem DIOP (Kagan H, Dang T.: J. Amer. Chem. Soc. 94, 6429 (1972).It is known that asymmetric homogeneous / hydrogenation is successfully carried out in the presence of Group 8 transition metal complexes which contain a chiral ligand in their coordination sphere. The highest optical yields were obtained with chiral diphosphine complexes prepared in situ from an olefinic complex, rhodium of the type Rh (en) 2 Cl 2 and 2,3-O-isopropylidene (or cyclohexylidene or cyclopentylidene) -2,3-dihydroxy- 1,4-bis (diphenylphosphino) butane. This diphosphine is known as DIOP (Kagan H, Dang T .: J. Amer. Chem. Soc. 94, 6429 (1972)).
Při použití katalyzátoru s (-)-DIOPem jako chirální složky se z N-acetylaminoskořicové kyseliny získává D-N-acetylfenylalanin (konfigurace R), zatímco k přípravě přírodního Lfenylalaninu (konfigurace S) je třeba použít (-j-)-DIOPu s obrácenou konfigurací na obou chirálních atomech uhlíku.When using a catalyst with (-) - DIOP as a chiral component, N-acetylamino-cinnamic acid yields DN-acetylphenylalanine (R configuration), while (-j -) - DIOP with the reverse configuration to both chiral carbon atoms.
Při syntéze (-)-DIOPu je klíčovým chirálním meziproduktem · 2,3-0-isopropyliden-Lthreitol, při jehož přípravě se vychází z kyseliny L-(+)-vinné, snadno dostupné z přírodního materiálu. Kyselinu D-(—)-vinnou naproti tomu je třeba získat štěpením racemické kyseliny vinné na optické antipody, přičemž příprava racemátů je sama o sobě obtížná (jde např. o hydroxylaci maleinové nebo fumarové kyseliny nebo o racemizaci L-(-j-)-vinné kyseliny).In the synthesis of (-) - DIOP, the key chiral intermediate is 2,3-O-isopropylidene-Lthreitol, prepared from L - (+) - tartaric acid, readily available from natural material. D - (-) - tartaric acid, on the other hand, is to be obtained by resolution of racemic tartaric acid into optical antipodes, the preparation of racemates being difficult in itself (eg hydroxylation of maleic or fumaric acid or racemization of L - (- j -) - tartaric acid).
Předmětem tohoto vynálezu je způsob přípravy 2,3-0-isopropyliden-2,3-dihydroxy-1 ,4bis(difenylfosfino)butan, jehož podstata spočívá v tom, že se na 2,3-0-isopropyliden-Dthreitol působí za teploty od —10 do +10 °C 4-toluensulfochloridem, výhodně v pyridinu, a pak natriumdifenylfosfinem při teplotě od 10 do 40 °C. Získaný produkt se použije k přípravě katalyzátoru asymetrické homogenní hydrogenace N-acylderivátů a, β — nenasycených α-aminokyselin na L-α — aminokyseliny.The present invention relates to a process for the preparation of 2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis (diphenylphosphino) butane, characterized in that 2,3-O-isopropylidene-Dthreitol is treated at a temperature of -10 to + 10 ° C with 4-toluenesulfochloride, preferably in pyridine, and then with sodium diphenylphosphine at a temperature of from 10 to 40 ° C. The product obtained is used to prepare a catalyst for asymmetric homogeneous hydrogenation of N-acyl derivatives of α, β-unsaturated α-amino acids to L-α-amino acids.
Reakce je blíže ilustrována následujícím schématem:The reaction is illustrated by the following scheme:
Vynález je blíže vysvětlen na následujícím příkladu provedení:The invention is illustrated by the following example:
PříkladExample
K roztoku 8,4 g isopropylidenthreitolu v 55 ml suchého pyridinu bylo při 0 °C přidáno 21 g rozetřeného 4-toluen-sulfochloridu najednou, směs byla třepána do rozpuštění a při 0 °C ponechána 12 hodin. Po nalití na led byly krystaly odsáty, promyty studeným etanolem a překrystalovány z etanolu. Bylo získáno 17,1 g produktu o 1.1. 92 až 94 °C /«/d20/ — 12,2 ° (C 3,5 CHC13). 2,3-0-isopropyliden-2,3dihydroxy-l,4-bis/difenylfosfino/butan.To a solution of 8.4 g of isopropylidenthreitol in 55 ml of dry pyridine at 0 ° C was added 21 g of triturated 4-toluenesulfochloride at once, the mixture was shaken until dissolved and kept at 0 ° C for 12 hours. After pouring on ice, the crystals were aspirated, washed with cold ethanol and recrystallized from ethanol. 17.1 g of the product of 1.1 were obtained. 92-94 ° C / "/ 20 d / - 12.2 ° (c 3.5 CHC1 3). 2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis (diphenylphosphino) butane.
Roztok 10 g ditosylátu ve 30 ml tetrahydrofuranu bylo po kapkách za míchání přidáván k roztoku natriumdifenylfosifnu. Po 2-hodinovém míchání byla sůl zfiltrována, promyta benzenem, filtrát zahuštěn a odparek přelit etanolem. Vyloučené krystaly byly rekrystalovány z etanolu, 1.1. 88 až 89 °C.A solution of 10 g of ditosylate in 30 ml of tetrahydrofuran was added dropwise with stirring to a solution of sodium diphenylphosphine. After stirring for 2 hours, the salt was filtered, washed with benzene, the filtrate was concentrated and the residue was poured over with ethanol. The precipitated crystals were recrystallized from ethanol, m.p. Mp 88-89 ° C.
PREDMET VYNÁLEZUOBJECT OF THE INVENTION
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS786684A CS201352B1 (en) | 1977-03-22 | 1978-10-13 | Process for preparing 2,3 -0-isopropyliden-2,3-dihydroxy-1,4-bis/diphenylphosphine/butane |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS190977A CS194386B1 (en) | 1977-03-22 | 1977-03-22 | Method of preparing 2,3-0-isopropylidene-d-threitol |
| CS786684A CS201352B1 (en) | 1977-03-22 | 1978-10-13 | Process for preparing 2,3 -0-isopropyliden-2,3-dihydroxy-1,4-bis/diphenylphosphine/butane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS201352B1 true CS201352B1 (en) | 1980-11-28 |
Family
ID=5354624
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS190977A CS194386B1 (en) | 1977-03-22 | 1977-03-22 | Method of preparing 2,3-0-isopropylidene-d-threitol |
| CS786684A CS201352B1 (en) | 1977-03-22 | 1978-10-13 | Process for preparing 2,3 -0-isopropyliden-2,3-dihydroxy-1,4-bis/diphenylphosphine/butane |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS190977A CS194386B1 (en) | 1977-03-22 | 1977-03-22 | Method of preparing 2,3-0-isopropylidene-d-threitol |
Country Status (1)
| Country | Link |
|---|---|
| CS (2) | CS194386B1 (en) |
-
1977
- 1977-03-22 CS CS190977A patent/CS194386B1/en unknown
-
1978
- 1978-10-13 CS CS786684A patent/CS201352B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS194386B1 (en) | 1979-12-31 |
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