CS274242B1 - Method of z-alkenes preparation - Google Patents
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- CS274242B1 CS274242B1 CS23489A CS23489A CS274242B1 CS 274242 B1 CS274242 B1 CS 274242B1 CS 23489 A CS23489 A CS 23489A CS 23489 A CS23489 A CS 23489A CS 274242 B1 CS274242 B1 CS 274242B1
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- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- DOSAIQAVEMTUDZ-UHFFFAOYSA-N [Li].NCCCN Chemical compound [Li].NCCCN DOSAIQAVEMTUDZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000007239 Wittig reaction Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 150000001299 aldehydes Chemical class 0.000 abstract description 7
- 241000238631 Hexapoda Species 0.000 abstract 1
- 241000607479 Yersinia pestis Species 0.000 abstract 1
- 239000003016 pheromone Substances 0.000 abstract 1
- 239000002585 base Substances 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- -1 aliphatic alcohols Chemical class 0.000 description 2
- YNKMHABLMGIIFX-UHFFFAOYSA-N benzaldehyde;methane Chemical compound C.O=CC1=CC=CC=C1 YNKMHABLMGIIFX-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BPNRCAKPBNDWPB-SREVYHEPSA-N 1-[(Z)-hex-1-enyl]-4-methylbenzene Chemical compound CCCC\C=C/c1ccc(C)cc1 BPNRCAKPBNDWPB-SREVYHEPSA-N 0.000 description 1
- BJVDVGYADREGEB-UHFFFAOYSA-M 10-hydroxydecyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCCCCCCCO)C1=CC=CC=C1 BJVDVGYADREGEB-UHFFFAOYSA-M 0.000 description 1
- 241000510032 Ellipsaria lineolata Species 0.000 description 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 description 1
- 239000000877 Sex Attractant Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- VAUKWMSXUKODHR-UHFFFAOYSA-M pentyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCC)C1=CC=CC=C1 VAUKWMSXUKODHR-UHFFFAOYSA-M 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- WRIKHQLVHPKCJU-UHFFFAOYSA-N sodium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([Na])[Si](C)(C)C WRIKHQLVHPKCJU-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Vynález se týká způsobu přípravy látek, obsahujících v molekule 1,2-disubstituovanou vazbu v Z uspořádání.The invention relates to a process for the preparation of substances containing a 1,2-disubstituted bond in the Z configuration.
Výše uvedené látky tvoří součást sexuálních feromonů některých druhů motýlů. Chemicky jsou to převážně alifatické alkoholy, acetáty nebo aldehydy s různým počtem uhlíkových atomů a jednou až třemi dvojnými vazbami v různých polohách a s různou geometrickou ieomerií včetně funkčních skupin.The above substances are part of the sexual pheromones of some butterfly species. Chemically, they are predominantly aliphatic alcohols, acetates, or aldehydes with different numbers of carbon atoms and one to three double bonds at different positions and with different geometrical isomerism including functional groups.
Dosud známé přípravy tohoto typu látek (Henrik C.A. a.j.Tetrahedron 33,1845 (l 977)) využívají většinou reakce alkalických solí acetylénů s alkylhalogenidy s následující redukcí trojné vazby na žádaný isomer vhodným výběrem reakčních podmínek (Rossi R., a.j.Synthesis 566(1977). Jiný způsob je založen na Wittigově reakci tj. reakci aldehydu s trifenylalkylfosfonium halogenidem za katalysy bází (Bestmann H.J.,a.j.Chem.Ber. 109,1694(1976). Výběrem reakčních podmínek lze dosáhnout většího nebo menšího procenta přítomnosti Z isomeru ve směsi. Nejoptimálnějěí výsledky z tohoto hlediska poskytuje methoda podle Bestmanna (Bestmann H.J.,a.j.Chem.Ber.109,1694(1976) využívající jako báze hexamethyldisilazidu natria, eventuálně reakce aldehydu s ylidem za nízkých teplot a přítomnost i hexamethylfosfortriamidu jako solvatačního činidla (Seebach D,,a.j.Helvetica Chim.Acta 65ř385(1982)), Nedávno byla publikována methoda využívající jako baze t-butylátu draselného a poskytující dosud nejvyšší procento Z isomeru (Vinczer P.,a.j.J.Chem.Ecol.11,1,113(1985). Uvedené methody poskytují 95 až 97 % Z isomeru ve směsi. Obecnou nevýhodou u těchto postupů je relativní nedostupnost báze, popřípadě používání karcinogemích rozpouštědel.The hitherto known preparations of this type of substance (Henrik CA and Tetrahedron 33, 1845 (1977)) utilize mostly the reaction of alkali salts of acetylenes with alkyl halides followed by reduction of the triple bond to the desired isomer by appropriate selection of reaction conditions (Rossi R., Synthesis 566 (1977). the method is based on the Wittig reaction, i.e., the reaction of the aldehyde with triphenylalkylphosphonium halide under base catalysis (Bestmann HJ, ajChem.Ber. 109, 1694 (1976). By selecting the reaction conditions a greater or lesser percentage of the Z isomer is present. In this regard, the Bestmann method (Bestmann HJ, ajChem.Ber.109,1694 (1976) using hexamethyldisilazide sodium as the base, eventually the reaction of an aldehyde with a ylide at low temperatures and the presence of hexamethylphosphoric triamide as a solvating agent (Seebach D, ajHelvetica Chim.Acta 65) R 385 (1982)), was recently published Methoda using as the base potassium t-butylate and yielding the highest percentage of Z isomer so far (Vinczer P., et al., Chem. Ec 11, 1113 (1985)). Said methods provide 95-97% of the isomer in the mixture. The general disadvantage of these processes is the relative unavailability of the base or the use of carcinogenic solvents.
Nyní bylo nalezeno, že pro generaci ylidu z Wittigovy soli je s výhodou možné používat lithné soli 1,3-úiaminopropanu, která je snadno dostupná, lze ji uchovávat po dlouhou dobu bez ztráty účinnosti a navíc poskytuje vysoké výtěžky Z-ieomerů.It has now been found that for the generation of the ylide from the Wittig salt, it is advantageously possible to use the 1,3-aminaminopropane lithium salt, which is readily available, can be stored for a long time without loss of efficacy, and additionally provides high yields of Z-isomers.
Předmětem předloženého vynálezu je způsob přípravy derivátů Z-alkenů obecného vzorce IIt is an object of the present invention to provide a process for preparing Z-alkene derivatives of formula (I)
R^HsCH-R2 (I) kde R3· je alkylová skupina s 1 až 7 atomy uhlíku, alkenyl s 2 až 7 atomy uhlíku, fenyl, nebo fenylalkyl s 1 až 4 atomy uhlíku v alkylové části a oR 3 is CH-R 2 (I) wherein R 3 is an alkyl group of 1 to 7 carbon atoms, alkenyl of 2 to 7 carbon atoms, phenyl, or phenylalkyl of 1 to 4 carbon atoms in the alkyl moiety and
R je alkyl s 1 až 8 atomy uhlíku, alkenyl s 3 až 8 atomy uhlíku, OJ-bydroxyalkyl, s 2 až 12 atomy uhlíku,R is alkyl of 1 to 8 carbon atoms, alkenyl of 3 to 8 carbon atoms, OO-hydroxyalkyl, 2 to 12 carbon atoms,
Wittigovou reakcí aldehydu obecného vzorce IIWittig reaction of the aldehyde of formula II
Í^-CHO (II) kde R1 má výše uvedený význam, se sloučeninou obecného vzorce IIIWherein R 1 is as defined above, with a compound of formula III
R2-CH2-P+ Ph-j X~ (III)R 2 -CH 2 -P + Ph-j X - (III)
CS 274242 Bl f kde R má výše uvedený význam, Ph je fenylová skupina a X je atom halogenu, která se vyznačuje tím, že se reakce provádí v přítomnosti lithium 1,3-diaminopropanu v tetrahydrofuranu, při teplotě -78 až 0 °C, s výhodou při -78 °C, potom se reakční směs rozloží běžně známým způsobem.EN 274 242 Bl f wherein R is as defined above, Ph is phenyl and X is halogen, which is characterized in that the reaction is carried out in the presence of lithium 1,3-diaminopropane in THF, at -78 to 0 ° C, preferably at -78 ° C, then the reaction mixture is decomposed in a manner known per se.
Lithium 1,3-diaminopropan se připraví rozpuštěním známého množství lithia v 1,3-diaminopropanu za normální teploty a do dalěí reakce se potom bere alikvotní díl. Bázi lze uchovávat v uzavřené skleněné baňce při teplotě O °C po dobu 3 měsíců beze ztráty účinnosti. Reakční postup je velmi jednoduchý a spočívá v prostém přlkapávání výše uvedené báze k suspenzi Wittigovy soli v tetrahydrofuranu s následujícím přikapáním aldehydu v témže rozpouštědle při teplotě -78 °C. Po ohřátí na teplotu místnosti se reakční směs rozloží vodou a zpracuje běžným způsobem. Reakční průběh lze sledovat pomocí tenkovrstvé chromatografie, stejný způsob je možné použít pro isolaoi produktů. Podle typu výchozího aldehydu bylo nalezeno, že produkt obsahuje 96 až 100 % Z isomerů.Lithium 1,3-diaminopropane is prepared by dissolving a known amount of lithium in 1,3-diaminopropane at normal temperature and then taking an aliquot into the next reaction. The base can be stored in a closed glass flask at 0 ° C for 3 months without loss of efficacy. The reaction procedure is very simple and involves simply dropping the above base to a suspension of the Wittig salt in tetrahydrofuran followed by dropwise addition of the aldehyde in the same solvent at -78 ° C. After warming to room temperature, the reaction mixture was quenched with water and worked up in a conventional manner. The reaction progress can be monitored by thin layer chromatography, the same method can be used for isolation of products. Depending on the type of starting aldehyde, the product was found to contain 96-100% of the isomers.
Vynález je blíže objasněn v následujících příkladech, které jej však žádným způsobem neomezují.The invention is illustrated in more detail by the following non-limiting examples.
Příklad 1Example 1
Příprava lithium 1,3-éiaminopropanu.Preparation of lithium 1,3-aminopropane.
150 mg (21,7 gat) lithiovóho drátu se nastříhá na oo nejmenši kousky a umístí do baňky s 8 ml čerstvě dest. 1,3-diaminopropanu. Potom se obsah míchá 1,5 h za laboratorní teploty. Během této doby se suspenze zbarví temně modře, což evědčí o vznikající soli. Po 1,5 h se vše odbarví na mléčně zakalený roztok potom se reakce dokončí zahříváním na 70 °C po dobu 1 h. Roztok se uchovává v této baňce pod septovým uzávěrem při teplotě 0 °C a do další reakce se bere alikvotní podíl.150 mg (21.7 g) of lithium wire is cut into small pieces and placed in a flask of 8 ml of fresh dest. 1,3-diaminopropane. The contents were then stirred at room temperature for 1.5 h. During this time, the suspension turns dark blue, indicating the formation of salts. After 1.5 h, the whole is decolorized to a milky solution then the reaction is completed by heating to 70 ° C for 1 h. The solution is stored in this flask under a septum cap at 0 ° C and an aliquot is taken for the next reaction.
Příklad 2Example 2
Příprava (Z)-l-(4-methylfenyl)-1-hexenu.Preparation of (Z) -1- (4-methylphenyl) -1-hexene.
K suspenzi pentyltrifenylfosfonium bromidu (240 mg; 0,5 mmol) v 4 ml tetrahydrofuranu (dest, ze sodného ketylu) se za chlazení na -60 °C a míchání pod argonem, přikape roztok připravený podle příkladu 1 (0,22 ml; 0,6 mmol). Vše se míchá dalších 20 min. při -60 °C a potom se přikape čerstvě dest tolylaldehyd (0,059 g; 0,5 mmol) v 0,5 ml tetrahydrofuranu. Reakční směs se nechá pozvolna zahřát na 0 °C a potom rozloží 0,2 ml vody. Organická vrstva se oddělí, vodná protřepe ještě 0,5 ml pentanu a potom se spojené organické podíly chromatografují na 20-ti násobku silikagelu.To a suspension of pentyltriphenylphosphonium bromide (240 mg; 0.5 mmol) in 4 mL of tetrahydrofuran (dest, sodium ketyl) was added dropwise the solution prepared as in Example 1 (0.22 mL; 0) while cooling to -60 ° C and stirring under argon. , 6 mmol). Stir for another 20 min. at -60 ° C and then dropwise addition of freshly tolylaldehyde (0.059 g; 0.5 mmol) in 0.5 mL of tetrahydrofuran. The reaction mixture was allowed to slowly warm to 0 ° C and then quenched with 0.2 mL of water. The organic layer was separated, the aqueous layer was shaken with 0.5 mL of pentane, and then the combined organics were chromatographed on 20 times silica gel.
Jako eluent byl použit čistý pentan. Po odpaření rozpouštědla bylo získáno 0,042 g (42 %) produktu. Analysou plynovou chromatografii byl zjištěn poměr isomerů Z : E = 96,4 : 3,6.IR,MS a HMR spektra jsou v souhlase s uvedenou strukturou.Pure pentane was used as eluent. After evaporation of the solvent, 0.042 g (42%) of the product was obtained. Gas chromatography analysis showed a ratio of Z: E = 96.4: 3.6 IR isomers. IR, MS and HMR spectra were consistent with the indicated structure.
CS 274242 BlCS 274242 Bl
Příklad 3Example 3
Příprava (10Z)-11-(4-methylfenyl)-10-undecen-l-oluPreparation of (10Z) -11- (4-methylphenyl) -10-undecen-1-ol
Postup byl stejný jako v příkladě 2 s tím rozdílem, že se jako Wittigova sůl použil 10-hydroxydecyltrifenylfosfonium bromid (0,047 g; 0,082 mmol) a roztok báze (0,06 ml; 0,164 mmol) připravené podle příkladu 1. Bylo získáno 0,018 g (86 %) produktu s obsahem 94 % Z isomeru IR,MS a NMR spektra jsou v souhlase s uvedenou strukturou.The procedure was the same as in Example 2 except that 10-hydroxydecyltriphenylphosphonium bromide (0.047 g; 0.082 mmol) and the base solution (0.06 mL; 0.164 mmol) prepared according to Example 1 were used as the Wittig's salt. 86%) of a product containing 94% of the Z isomer of IR, MS and NMR spectra are consistent with the indicated structure.
Příklad 4Example 4
Příprava (Z)-lO-tridecen-l-oluPreparation of (Z) -110-tridecen-1-ol
Postup byl stejný jako v příkladě 3 s tím rozdílem, že se místo tolylaldehydu použil propanal (0,021 ml; 0,37 mmol). Bylo získáno 20 mg (30 %) produktu, který obsahoval 98,7 % Z isomeru IR,MS a NMR spektra jsou v souhlase s uvedenou strukturou.The procedure was the same as in Example 3 except that propanal (0.021 mL; 0.37 mmol) was used instead of tolylaldehyde. 20 mg (30%) of the product containing 98.7% of the IR isomer was obtained, MS and NMR spectra were consistent with the structure.
Příklad 5Example 5
Příprava (lOZ,12E)-lO,12-tetradekadien-l-oluPreparation of (10D, 12E) -1,10,12-tetradecadien-1-ol
Postupovalo se podle příkladu 4 s tím rozdílem, že se místo propenalu použil (E)-2-buten-l-al (0,021 g; 0,3 mmol). Výtěžek byl 0,02 g (61 %). Plenovou chromatografií nebyl identifikován žádný (10E,12E)-isomer IR,MS a NMR spektra jsou v souhlase a uvedenou strukturou.Example 4 was followed except that (E) -2-buten-1-al (0.021 g; 0.3 mmol) was used instead of propenal. The yield was 0.02 g (61%). No (10E, 12E) -isomer of IR, MS, and NMR spectra were found to be consistent with the indicated structure by MLC.
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| CS23489A CS274242B1 (en) | 1989-01-13 | 1989-01-13 | Method of z-alkenes preparation |
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| Elfehail et al. | . alpha.-Nitro ketones. 5. Synthesis of 2-nitrocyclopentanones | |
| Mukaiyama et al. | A New and Effective Asymmetric Synthesis of 3-Phenylalkanals | |
| Blumbergs et al. | Synthesis and stereochemistry of syn-and anti-p-nitrophenyl phenacyl methylphosphonate oxime | |
| Crombie et al. | The synthesis of terminal enynes by Grignard additions to pyridazine 1-oxide |