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【结 构 式】 
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【分子编号】10386 【品名】Allyl(bromo)magnesium 【CA登记号】1730-25-2 |
【 分 子 式 】C3H5BrMg 【 分 子 量 】145.2817 【元素组成】C 24.8% H 3.47% Br 55% Mg 16.73% |
合成路线1
该中间体在本合成路线中的序号：(VI)The enantioselective condensation of 3-(trimethylsilyl)propynal (V) with allylmagnesium bromide (VI) by means of (+)-Ipc2B-OMe as chiral catalyst gives hex-5-en-1-yn-3(R)-ol (VII), which is silylated with Tbdps-Cl and imidazole to yield the silyl ether (VIII). The oxidation of the terminal double bond of (VII) by means of OsO4 and NaIO4 affords the aldehyde (IX), which is submitted to a Wittig condensation with the phosphorane (X) in benzene to provide the unsaturated ester (XI). The enantioselective dihydroxylation of the double bond of (XI) with AD-mix-beta in tert-butanol/water gives the dihydroxyester (XII), which is protected with 2-methoxypropene (XIII) and PPTS to yield the isopropylidene ketal (XIV). The bromination of the triple bond of (XIV), followed by selective hydrogenation, affords the cis-bromovinyl compound (XV), whose ester group is reduced with LiAlH4 in THF to provide the primary alcohol (XVI). The oxidation of (XVI) with (COCl)2 and TEA in DMSO gives the carbaldehyde (XVII), which is submitted to a Wittig condensation with the phosphorane (XVIII) in hot dichloromethane to yield the diunsaturated aldehyde (XIX). The enantioselective condensation of aldehyde (XIX) with allylmagnesium bromide catalyzed by (+)Ipc2-B-OMe affords the chiral alcohol (XX), which is esterified with acryloyl chloride (XXI) and DIEA in dichloromethane to provide the ester (XXII). Compound (XXII) is submitted to a ring-closing metathesis catalyzed by a Rh catalyst (Grubbs's catalyst), yielding the dihydropyran derivative (XXIII), which is submitted to cleavage of the acetonide group by means of Montmorillonite K 10 to afford the diol (XXIV). The condensation of the bromovinyl group of (XXIV) with the intermediate boronic ester (IV) by means of Pd(PPh3)4 and Ag2O gives compound (XXV) with the complete backbone of the target fostriecin. The selective monosilylation of (XXV) with Tbdps-OTf gives the intermediate (XXVI).
| 【1】 Falck, J.R.; Reddy, Y.K.; Asymmetric total synthesis of (+)-fostriecin. Org Lett 2002, 4, 6, 969. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (IV) | 55458 | tert-butyl(diphenyl){[(2E,4Z)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,4-pentadienyl]oxy}silane; tert-butyl(diphenyl)silyl (2E,4Z)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,4-pentadienyl ether | C27H37BO3Si | 详情 | 详情 | |
| (V) | 20043 | 3-(trimethylsilyl)-2-propynal | C6H10OSi | 详情 | 详情 | |
| (VI) | 10386 | Allyl(bromo)magnesium | 1730-25-2 | C3H5BrMg | 详情 | 详情 |
| (VII) | 55459 | (3R)-5-hexen-1-yn-3-ol | C6H8O | 详情 | 详情 | |
| (VIII) | 55460 | tert-butyl(diphenyl)silyl (1R)-1-ethynyl-3-butenyl ether; tert-butyl{[(1R)-1-ethynyl-3-butenyl]oxy}diphenylsilane | C22H26OSi | 详情 | 详情 | |
| (IX) | 55461 | (3R)-3-{[tert-butyl(diphenyl)silyl]oxy}-4-pentynal | C21H24O2Si | 详情 | 详情 | |
| (X) | 37071 | ethyl 2-(triphenylphosphoranylidene)propanoate | 5717-37-3 | C23H23O2P | 详情 | 详情 |
| (XI) | 55462 | ethyl (E,5R)-5-{[tert-butyl(diphenyl)silyl]oxy}-2-methyl-2-hepten-6-ynoate | C26H32O3Si | 详情 | 详情 | |
| (XII) | 55463 | ethyl (2S,3R,5R)-5-{[tert-butyl(diphenyl)silyl]oxy}-2,3-dihydroxy-2-methyl-6-heptynoate | C26H34O5Si | 详情 | 详情 | |
| (XIII) | 17354 | isopropenyl methyl ether; 2-methoxy-1-propene | 116-11-0 | C4H8O | 详情 | 详情 |
| (XIV) | 55464 | ethyl (4S,5R)-5-((2R)-2-{[tert-butyl(diphenyl)silyl]oxy}-3-butynyl)-2,2,4-trimethyl-1,3-dioxolane-4-carboxylate | C29H38O5Si | 详情 | 详情 | |
| (XV) | 55465 | ethyl (4S,5R)-5-((2R,3Z)-4-bromo-2-{[tert-butyl(diphenyl)silyl]oxy}-3-butenyl)-2,2,4-trimethyl-1,3-dioxolane-4-carboxylate | C29H39BrO5Si | 详情 | 详情 | |
| (XVI) | 55466 | [(4R,5R)-5-((2R,3Z)-4-bromo-2-{[tert-butyl(diphenyl)silyl]oxy}-3-butenyl)-2,2,4-trimethyl-1,3-dioxolan-4-yl]methanol | C27H37BrO4Si | 详情 | 详情 | |
| (XVII) | 55467 | (4S,5R)-5-((2R,3Z)-4-bromo-2-{[tert-butyl(diphenyl)silyl]oxy}-3-butenyl)-2,2,4-trimethyl-1,3-dioxolane-4-carbaldehyde | C27H35BrO4Si | 详情 | 详情 | |
| (XVIII) | 55468 | 2-(triphenylphosphoranylidene)acetaldehyde | C20H17OP | 详情 | 详情 | |
| (XIX) | 55469 | (E)-3-[(4R,5R)-5-((2R,3Z)-4-bromo-2-{[tert-butyl(diphenyl)silyl]oxy}-3-butenyl)-2,2,4-trimethyl-1,3-dioxolan-4-yl]-2-propenal | C29H37BrO4Si | 详情 | 详情 | |
| (XX) | 55470 | (1E,3R)-1-[(4R,5R)-5-((2R,3Z)-4-bromo-2-{[tert-butyl(diphenyl)silyl]oxy}-3-butenyl)-2,2,4-trimethyl-1,3-dioxolan-4-yl]-1,5-hexadien-3-ol | C32H43BrO4Si | 详情 | 详情 | |
| (XXI) | 11577 | Acryloyl chloride; Acrylyl chloride;2-Propenoyl chloride | 814-68-6 | C3H3ClO | 详情 | 详情 |
| (XXII) | 55471 | (1R)-1-{(E)-2-[(4R,5R)-5-((2R,3Z)-4-bromo-2-{[tert-butyl(diphenyl)silyl]oxy}-3-butenyl)-2,2,4-trimethyl-1,3-dioxolan-4-yl]ethenyl}-3-butenyl acrylate | C35H45BrO5Si | 详情 | 详情 | |
| (XXIII) | 55472 | (6R)-6-{(E)-2-[(4R,5R)-5-((2R,3Z)-4-bromo-2-{[tert-butyl(diphenyl)silyl]oxy}-3-butenyl)-2,2,4-trimethyl-1,3-dioxolan-4-yl]ethenyl}-5,6-dihydro-2H-pyran-2-one | C33H41BrO5Si | 详情 | 详情 | |
| (XXIV) | 55473 | (6R)-6-((1E,3R,4R,6R,7Z)-8-bromo-6-{[tert-butyl(diphenyl)silyl]oxy}-3,4-dihydroxy-3-methyl-1,7-octadienyl)-5,6-dihydro-2H-pyran-2-one | C30H37BrO5Si | 详情 | 详情 | |
| (XXV) | 55474 | (6R)-6-((1E,3R,4R,6R,7Z,9Z,11E)-6,13-bis{[tert-butyl(diphenyl)silyl]oxy}-3,4-dihydroxy-3-methyl-1,7,9,11-tridecatetraenyl)-5,6-dihydro-2H-pyran-2-one | C51H62O6Si2 | 详情 | 详情 | |
| (XXVI) | 55475 | (6R)-6-((1E,3R,4R,6R,7Z,9Z,11E)-3,6,13-tris{[tert-butyl(diphenyl)silyl]oxy}-4-hydroxy-3-methyl-1,7,9,11-tridecatetraenyl)-5,6-dihydro-2H-pyran-2-one | C67H80O6Si3 | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(VIII)Delmopinol can be obtained by three different ways: 1) The reaction of 2-(benzylamino)-6-propylnonan-1-ol (I) with ethylene oxide (II) in ethanol at 100 C yields the corresponding N-(2-hydroxyethyl)derivative (III), which is cyclized with H2SO4 at 140-150 C to 4-benzyl-3-(4-propylheptyl)morpholine (IV). The debenzylation of (IV) by hydrogenolysis with H2 over Pd/C affords the free morpholine (V), which is finally condensed with 2-chloroethanol (VI) by means of KI and KOH in refluxing ethanol. 2) The Grignard condensation of 4-heptanone (VII) with allyl bromide (VIII) in ethyl ether gives 4-propyl-1-hepten-4-ol (IX), which is cyclocondensed with morpholine (X) by means of H2O2 and Na2WO4 in methanol to yield 4-(perhydroisoxazol[3,2-c][1,4]oxazin-2-ylmethyl)-4-heptanol (XI). Reductive ring opening of (XI) by hydrogenation with H2 over Pd/C and p-toluenesulfonic acid in isopropanol affords a mixture of the morpholine (V) and the hydroxymorpholine (XII). This mixture, without separation, is treated first with SOCl2 in chloroform to perform Cl-OH interchange, then with NaOH to obtain the corresponding double bond, and finally, the mixture is hydrogenated with H2 over Ra-nickel and triethylamine in dioxane in order to obtain pure (V), already obtained. 3) The acylation of the alkylmorpholine (V) with oxalic acid monomethyl ester (XIII) by means of triethylamine in refluxing benzene gives the corresponding condensation compound (XIV), which is then reduced with LiAlH4 in refluxing ethyl ester.
| 【1】 Mealy, N.; Ngo, J.; Castaner, J.; Delmopinol Hydrochloride. Drugs Fut 1996, 21, 8, 787. |
| 【2】 (Ferrosan AB); New morpholino cpds. their process of preparation and medicines containing them. BE 0888052; BE 0901496 . |
| 【3】 Hernestam, S.; Thelin, B.; Seifert, E.; Nilsson, A. (Pharmacia & Upjohn AB); Substd. isoxazolidines and isoxazolines. WO 9014342 . |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (I) | 10380 | 2-(Benzylamino)-6-propyl-1-nonanol | C19H33NO | 详情 | 详情 | |
| (II) | 10393 | Oxirane; Ethylene oxide | 75-21-8 | C2H4O | 详情 | 详情 |
| (III) | 10381 | 2-[Benzyl(2-hydroxyethyl)amino]-6-propyl-1-nonanol | C21H37NO2 | 详情 | 详情 | |
| (IV) | 10382 | 4-Benzyl-3-(4-propylheptyl)morpholine | C21H35NO | 详情 | 详情 | |
| (V) | 10383 | 3-(4-Propylheptyl)morpholine | C14H29NO | 详情 | 详情 | |
| (VI) | 10384 | 2-Chloro-1-ethanol; Ethylene chlorohydrin | 107-07-3 | C2H5ClO | 详情 | 详情 |
| (VII) | 10385 | 4-Heptanone; Dipropyl ketone | 123-19-3 | C7H14O | 详情 | 详情 |
| (VIII) | 10386 | Allyl(bromo)magnesium | 1730-25-2 | C3H5BrMg | 详情 | 详情 |
| (IX) | 10387 | 4-Propyl-1-hepten-4-ol | C10H20O | 详情 | 详情 | |
| (X) | 10388 | Morpholine | 110-91-8 | C4H9NO | 详情 | 详情 |
| (XI) | 10389 | 4-(Hexahydroisoxazolo[3,2-c][1,4]oxazin-2-ylmethyl)-4-heptanol | C14H27NO3 | 详情 | 详情 | |
| (XII) | 10390 | 1-(1,4-Oxazinan-3-yl)-4-propyl-2-heptanol | C14H29NO2 | 详情 | 详情 | |
| (XIII) | 10391 | 2-Methoxy-2-oxoacetic acid | C3H4O4 | 详情 | 详情 | |
| (XIV) | 10392 | 2-Oxo-2-[3-(4-propylheptyl)morpholino]acetic acid | C16H29NO4 | 详情 | 详情 |
合成路线3
该中间体在本合成路线中的序号：The Grignard reaction of aldehyde (XVII) with allylmagnesium bromide in presence of ZnCl2, followed by protection of the resulting alcohol with benzyloxymethyl chloride (Bom-Cl) gives the intermediate (XVIII), which by desilylation of NH4F; cleavage of the cyclic carbonate with Ph-Li and acylation of the OH group with Ac2O yields the benzoate ester (XIX). The transposition of the acetoxyketone grouping, catalyzed by the cyclic guanidine (XX) provides (XXI) with the correct stereochemistry of taxol. The ozonolysis of the terminal double bond of (XXI) gives aldehyde (XXII), which is cyclized by means of DMAP in dichloromethane yielding the tricyclic alcohol (XXIII). The protection of the OH group of (XXIII) with 2,2,2-trichloroethyl chloroformate (Troc-Cl) affords the expected carbonate (XXIV), which is treated with NaI and HCl in order to eliminate the Bom protecting group to give the secondary alcohol (XXV). The reaction of (XXV) with Ms-Cl yields the mesylate (XXVI), which by reaction with LiBr is converted into the bromide (XXVII). The oxidation of (XXVII) with OsO4, followed by a treatment with triphosgene affords the glycol (XXVIII), which is cyclized with means of KCN and DIEA and acetylated with Ac2O providing (XXIX) with the oxetane ring of taxol.
| 【1】 Wender, P.A.; et al.; The pinene path to taxanes. 6. Concise stereocontrolled synthesis of Taxol. J Am Chem Soc 1997, 119, 11, 2757. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| 10386 | Allyl(bromo)magnesium | 1730-25-2 | C3H5BrMg | 详情 | 详情 | |
| (XVII) | 35345 | 2-[(1S,5S,6S,7S,8S,12S)-7,11,14,14-tetramethyl-3,9-dioxo-8-[(triethylsilyl)oxy]-12-[(triisopropylsilyl)oxy]-2,4-dioxatricyclo[8.3.1.0(1,5)]tetradec-10-en-6-yl]acrylaldehyde | C34H58O7Si2 | 详情 | 详情 | |
| (XVIII) | 35346 | (1S,5S,6S,7S,8S,12S)-6-[(2R)-2-[(benzyloxy)methoxy]-1-methylene-4-pentenyl]-7,11,14,14-tetramethyl-8-[(triethylsilyl)oxy]-12-[(triisopropylsilyl)oxy]-2,4-dioxatricyclo[8.3.1.0(1,5)]tetradec-10-ene-3,9-dione | C45H72O8Si2 | 详情 | 详情 | |
| (XIX) | 35347 | C47H66O9Si | 详情 | 详情 | ||
| (XX) | 35348 | 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine | C7H13N3 | 详情 | 详情 | |
| (XXI) | 35349 | (1S,2S,3S,4S,6R,9S)-6-(acetoxy)-3-[(2R)-2-[(benzyloxy)methoxy]-1-methylene-4-pentenyl]-1-hydroxy-4,8,11,11-tetramethyl-5-oxo-9-[(triisopropylsilyl)oxy]bicyclo[5.3.1]undec-7-en-2-yl benzoate | C47H66O9Si | 详情 | 详情 | |
| (XXII) | 35350 | (1S,2S,3S,4S,6R,9S)-6-(acetoxy)-3-(1-[(1R)-1-[(benzyloxy)methoxy]-3-oxopropyl]vinyl)-1-hydroxy-4,8,11,11-tetramethyl-5-oxo-9-[(triisopropylsilyl)oxy]bicyclo[5.3.1]undec-7-en-2-yl benzoate | C46H64O10Si | 详情 | 详情 | |
| (XXIII) | 35351 | (1S,2S,3R,5R,7S,8S,10R,13S)-10-(acetoxy)-5-[(benzyloxy)methoxy]-1,7-dihydroxy-8,12,15,15-tetramethyl-4-methylene-9-oxo-13-[(triisopropylsilyl)oxy]tricyclo[9.3.1.0(3,8)]pentadec-11-en-2-yl benzoate | C46H64O10Si | 详情 | 详情 | |
| (XXIV) | 35352 | (1S,2S,3R,5R,7S,8S,10R,13S)-10-(acetoxy)-5-[(benzyloxy)methoxy]-1-hydroxy-8,12,15,15-tetramethyl-4-methylene-9-oxo-7-[[(2,2,2-trichloroethoxy)carbonyl]oxy]-13-[(triisopropylsilyl)oxy]tricyclo[9.3.1.0(3,8)]pentadec-11-en-2-yl benzoate | C49H65Cl3O12Si | 详情 | 详情 | |
| (XXV) | 35353 | (1S,2S,3R,5R,7S,8S,10R,13S)-10-(acetoxy)-1,5-dihydroxy-8,12,15,15-tetramethyl-4-methylene-9-oxo-7-[[(2,2,2-trichloroethoxy)carbonyl]oxy]-13-[(triisopropylsilyl)oxy]tricyclo[9.3.1.0(3,8)]pentadec-11-en-2-yl benzoate | C41H57Cl3O11Si | 详情 | 详情 | |
| (XXVI) | 35354 | (1S,2S,3R,5R,7S,8S,10R,13S)-10-(acetoxy)-1-hydroxy-8,12,15,15-tetramethyl-5-[[methyl(dimethylene)-lambda(6)-sulfanyl]oxy]-4-methylene-9-oxo-7-[[(2,2,2-trichloroethoxy)carbonyl]oxy]-13-[(triisopropylsilyl)oxy]tricyclo[9.3.1.0(3,8)]pentadec-11-en-2- | C44H63Cl3O11SSi | 详情 | 详情 | |
| (XXVII) | 35355 | (1S,2S,3S,5S,7S,8S,10R,13S)-10-(acetoxy)-5-bromo-1-hydroxy-8,12,15,15-tetramethyl-4-methylene-9-oxo-7-[[(2,2,2-trichloroethoxy)carbonyl]oxy]-13-[(triisopropylsilyl)oxy]tricyclo[9.3.1.0(3,8)]pentadec-11-en-2-yl benzoate | C41H56BrCl3O10Si | 详情 | 详情 | |
| (XXVIII) | 35356 | (1S,5S,6R,7S,8S,10S,11S,13R,16S)-8-bromo-7-hydroxy-7-(hydroxymethyl)-11,15,18,18-tetramethyl-3,12-dioxo-10-[[(2,2,2-trichloroethoxy)carbonyl]oxy]-16-[(triisopropylsilyl)oxy]-2,4-dioxatetracyclo[12.3.1.0(1,5).0(6,11)]octadec-14-en-13-yl acetate | C35H52BrCl3O12Si | 详情 | 详情 | |
| (XXIX) | 35357 | (1S,5S,6R,10R,12S,13S,15R,18S)-15-(acetoxy)-13,17,20,20-tetramethyl-3,14-dioxo-12-[[(2,2,2-trichloroethoxy)carbonyl]oxy]-18-[(triisopropylsilyl)oxy]-2,4,9-trioxapentacyclo[14.3.1.0(1,5).0(6,13).0(7,10)]icos-16-en-7-yl acetate | C37H53Cl3O13Si | 详情 | 详情 |
合成路线4
该中间体在本合成路线中的序号：(XXVI)The chiral aldehyde (XI) can also be obtained as follows: The reaction of dodecanal (XXV) with allylmagnesium bromide (XXVI) in THF gives 1-pentadecen-4-ol (XXVII) as a racemic mixture, which is esterified with 2(R)-acetoxy-2-phenylacetic acid (XXVIII) by means of dicyclohexylcarbodiimide (DCC) and dimethylaminopyridine (DMAP) to yield the diastereoisomeric mixture of esters (XXIX) and (XXX), which are separated by flash chromatography. The hydrolysis of (XXIX) and (XXX) with KOH in methanol affords the alcohols (XXXI) and (XXXII). The unwanted isomer (XXXII) can be isomerized to (XXXI) through the formation of the 4-nitrobenzoyl ester and hydrolysis with K2CO3. The benzylation of (XXXI) with benzyl bromide and KH in THF gives the benzyl ether (XXXIII), which is finally ozonolyzed to the desired aldehyde (XI) with O3 in methanol-dichloromethane.
| 【1】 Prous, J.; Mealy, N.; Castaner, J.; Orlistat. Drugs Fut 1994, 19, 11, 1003. |
| 【2】 Tehim, A.; Chen, P.; Hanessian, S.; Total synthesis of (-)-tetrahydrolipstatin. J Org Chem 1993, 58, 27, 7768-81. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XI) | 11068 | (3R)-3-(Benzyloxy)tetradecanal | C21H34O2 | 详情 | 详情 | |
| (XXV) | 11082 | Lauraldehyde; Dodecanal | 112-54-9 | C12H24O | 详情 | 详情 |
| (XXVI) | 10386 | Allyl(bromo)magnesium | 1730-25-2 | C3H5BrMg | 详情 | 详情 |
| (XXVII) | 11084 | 1-Pentadecen-4-ol | C15H30O | 详情 | 详情 | |
| (XXVIII) | 11085 | (2R)-3-Methoxy-3-oxo-2-phenylpropionic acid | C10H10O4 | 详情 | 详情 | |
| (XXIX) | 11086 | 1-methyl 3-[(1R)-1-undecyl-3-butenyl] (2S)-2-phenylpropanedioate | C25H38O4 | 详情 | 详情 | |
| (XXX) | 11087 | 1-methyl 3-[(1S)-1-undecyl-3-butenyl] (2S)-2-phenylpropanedioate | C25H38O4 | 详情 | 详情 | |
| (XXXI) | 11088 | (4R)-1-Pentadecen-4-ol | C15H30O | 详情 | 详情 | |
| (XXXII) | 11089 | (4S)-1-Pentadecen-4-ol | C15H30O | 详情 | 详情 | |
| (XXXIII) | 11090 | (4R)-4-(Benzyloxy)-1-pentadecene; Benzyl (1R)-1-undecyl-3-butenyl ether | C22H36O | 详情 | 详情 |
合成路线5
该中间体在本合成路线中的序号：(IV)The reaction of N-Boc-L-isoleucine (I) with O-methylhydroxylamine (II) by means of PyBOP gives the corresponding amide (III), which is condensed with allylmagnesium bromide (IV) to afford the octenone (V). The reduction of (V) with NaBH4 yields the carbinol (VI), which is N- and O-methylated with Me-I and NaH to provide the dimethylated compound (VII). Finally, the terminal double bond of (VII) is oxidated by means of NaIO4 and RuO2 to furnish the desired intermediate, the amino acid (VIII).
| 【1】 Roux, F.; et al.; Synthesis of dolastatin-10 and [R-Doe]-dolastatin-10. Tetrahedron 1994, 50, 18, 5345. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (I) | 30009 | (2S,3S)-2-[(tert-butoxycarbonyl)amino]-3-methylpentanoic acid | 13139-16-7 | C11H21NO4 | 详情 | 详情 |
| (II) | 13361 | (Methoxyamino)methane; N,O-Dimethylhydroxylamine | 1117-97-1 | C2H7NO | 详情 | 详情 |
| (III) | 38788 | tert-butyl (1S,2S)-1-[[methoxy(methyl)amino]carbonyl]-2-methylbutylcarbamate | 3350-19-4 | C13H26N2O4 | 详情 | 详情 |
| (IV) | 10386 | Allyl(bromo)magnesium | 1730-25-2 | C3H5BrMg | 详情 | 详情 |
| (V) | 54596 | tert-butyl (1S)-1-(sec-butyl)-2-oxo-4-pentenylcarbamate | C14H25NO3 | 详情 | 详情 | |
| (VI) | 54597 | tert-butyl (1S,2R)-1-(sec-butyl)-2-hydroxy-4-pentenylcarbamate | C14H27NO3 | 详情 | 详情 | |
| (VII) | 54598 | tert-butyl (1S,2R)-1-(sec-butyl)-2-methoxy-4-pentenyl(methyl)carbamate | C16H31NO3 | 详情 | 详情 | |
| (VIII) | 54599 | (3R,4S)-4-[(tert-butoxycarbonyl)(methyl)amino]-3-methoxy-5-methylheptanoic acid | C15H29NO5 | 详情 | 详情 |
合成路线6
该中间体在本合成路线中的序号：(III)The reduction of the protected (S)-ethyl lactate (I) with DIBAL in dichloromethane gives the aldehyde (II), which by a Grignard condensation with allylmagnesium bromide (III) in ethyl ether yields the homoallylic alcohol (IV). The reaction of (IV) with Tbdms-Cl and imidazole in DMF affords the silyl ether (V), which is ozonolyzed with O3 in dichloromethane/methanol to provide the aldehyde (VI), which, by a new Grignard condensation with isopropenylmagnesium bromide (VII) in THF, gives the allyl alcohol derivative (VIII). Compound (VIII) is treated with triethyl orthoacetate (refluxing xylene) in a Johnson Claisen rearrangement to yield the (E)-unsaturated ester (IX), which is debenzylated by treatment with DDQ to afford the secondary alcohol (X). The oxidation of (X) with oxalyl chloride provides the ketoester (XI), which is oxidized with AD-mix beta in tert-butanol/water to furnish the diol (XII) as an inseparable mixture of isomers. This mixture, by a Wittig condensation with the phosphonium salt (XIII) and KHMDS in THF, gives a mixture of the hydroxylactones (XIV) and (XV) that are separated by chromatography. Compound (XIV) is mesylated with MsCl and TEA and treated with K2CO3 in methanol to give the desired epoxyester (XVI). The diastereomer (XV) with wrong configuration is recovered by a double inversion: Compound (XV) is mesylated and the resulting derivative is then epoxidated with K2CO3 in methanol to yield the epoxide (XVII), which is treated with K2CO3 in methanol/water to afford the hydroxylactone (XIV) with the adequate configuration.
| 【1】 Martin, H.J.; et al.; How stable are epoxides? A novel synthesis of epothilone B. Angew Chem. Int Ed Engl 2000, 39, 3, 581. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (I) | 49259 | ethyl (2S)-2-[(4-methoxybenzyl)oxy]propanoate | C13H18O4 | 详情 | 详情 | |
| (II) | 49260 | (2S)-2-[(4-methoxybenzyl)oxy]propanal | C11H14O3 | 详情 | 详情 | |
| (III) | 10386 | Allyl(bromo)magnesium | 1730-25-2 | C3H5BrMg | 详情 | 详情 |
| (IV) | 49261 | (2S,3S)-2-[(4-methoxybenzyl)oxy]-5-hexen-3-ol | C14H20O3 | 详情 | 详情 | |
| (V) | 49262 | tert-butyl[((1S)-1-[(1S)-1-[(4-methoxybenzyl)oxy]ethyl]-3-butenyl)oxy]dimethylsilane; tert-butyl(dimethyl)silyl (1S)-1-[(1S)-1-[(4-methoxybenzyl)oxy]ethyl]-3-butenyl ether | C20H34O3Si | 详情 | 详情 | |
| (VI) | 49263 | (3S,4S)-3-[[tert-butyl(dimethyl)silyl]oxy]-4-[(4-methoxybenzyl)oxy]pentanal | C19H32O4Si | 详情 | 详情 | |
| (VII) | 43649 | bromo(isopropenyl)magnesium；isopropenyl magnesium bromide；1-Methylvinylmagnesiumbromide;1-Propen-2-ylmagnesium bromide;a-Methylvinylmagnesium bromide | 13291-18-4 | C3H5BrMg | 详情 | 详情 |
| (VIII) | 49264 | (5S,6S)-5-[[tert-butyl(dimethyl)silyl]oxy]-6-[(4-methoxybenzyl)oxy]-2-methyl-1-hepten-3-ol | C22H38O4Si | 详情 | 详情 | |
| (IX) | 49265 | ethyl (E,7S,8S)-7-[[tert-butyl(dimethyl)silyl]oxy]-8-[(4-methoxybenzyl)oxy]-4-methyl-4-nonenoate | C26H44O5Si | 详情 | 详情 | |
| (X) | 49266 | ethyl (E,7S,8S)-7-[[tert-butyl(dimethyl)silyl]oxy]-8-hydroxy-4-methyl-4-nonenoate | C18H36O4Si | 详情 | 详情 | |
| (XI) | 49267 | ethyl (E,7S)-7-[[tert-butyl(dimethyl)silyl]oxy]-4-methyl-8-oxo-4-nonenoate | C18H34O4Si | 详情 | 详情 | |
| (XII) | 49268 | ethyl (7S)-7-[[tert-butyl(dimethyl)silyl]oxy]-4,5-dihydroxy-4-methyl-8-oxononanoate | C18H36O6Si | 详情 | 详情 | |
| (XIII) | 40820 | tributyl[(2-methyl-1,3-thiazol-4-yl)methyl]phosphonium chloride | C17H33ClNPS | 详情 | 详情 | |
| (XIV) | 49269 | (5R)-5-[(1R,3S,4E)-3-[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-4-methyl-5-(2-methyl-1,3-thiazol-4-yl)-4-pentenyl]-5-methyldihydro-2(3H)-furanone | C21H35NO4SSi | 详情 | 详情 | |
| (XV) | 49270 | (5S)-5-[(1S,3S,4E)-3-[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-4-methyl-5-(2-methyl-1,3-thiazol-4-yl)-4-pentenyl]-5-methyldihydro-2(3H)-furanone | C21H35NO4SSi | 详情 | 详情 | |
| (XVI) | 49271 | methyl 3-[(2R,3S)-3-[(2S,3E)-2-[[tert-butyl(dimethyl)silyl]oxy]-3-methyl-4-(2-methyl-1,3-thiazol-4-yl)-3-butenyl]-2-methyloxiranyl]propanoate | C22H37NO4SSi | 详情 | 详情 | |
| (XVII) | 49272 | methyl 3-[(2S,3R)-3-[(2S,3E)-2-[[tert-butyl(dimethyl)silyl]oxy]-3-methyl-4-(2-methyl-1,3-thiazol-4-yl)-3-butenyl]-2-methyloxiranyl]propanoate | C22H37NO4SSi | 详情 | 详情 |
合成路线7
该中间体在本合成路线中的序号：(VIII)The reaction of 4-fluorophenol (I) with epichlorohydrin (II) by means of K2CO3 in refluxing acetone gives 2-(4-fluorophenoxymethyl)oxirane (III), which is submitted to an enantioselective ring opening with the Jacobsen (R,R)-catalyst yielding a mixture of the (R)-diol (IV) and unaltered epoxide (V), easily separated by column chromatography. The reaction of (IV) with tosyl chloride and pyridine in dichloromethane affords the primary monotosylate (VI), which is converted into the chiral epoxide (VII) by reaction with NaH in THF/DMF. The reaction of (VII) with allylmagnesium bromide (VIII) in ethyl ether gives the 2-hexenol derivative (IX), which is treated with benzenesulfonyl chloride and DMAP yielding the sulfonate (X). The ozonolysis of (X) with ozone in dichloromethane affords the aldehyde (XI), which is condensed with ethoxycarbonylmethylene(triphenyl)phosphorane (XII) yielding the 2-heptenoic ester (XIII). The reduction of (XIII) with diisobutylaluminum hydride (DIBAL) in toluene/dichloromethane provides the 2-hepten-1-ol (XIV), which is epoxidized with cumene hydroperoxide in the presence of diisopropyl (+)-tartrate and Ti(Oi-Pr)4 in dichloromethane to give the chiral epoxyalcohol (XV). The reaction of (XV) with triphenylphosphine/CCl4 in chloroform affords the corresponding chloride (XVI).
| 【1】 Adhikari, S.S.; Hymavathi, L.; Sadalapure, K.; Sharma, G.V.M.; Sreenivas, P.; Mhaskar, S.V.; Lalitha, S.V.S.; Chorghade, M.S.; Murugaiah, A.M.S.; Prasad, T.R.; Reddy, B.S.; Gurjar, M.K.; Reddy, V.G.; Krishna, P.R. (LeukoSite, Inc.); Substd. oxygen alicyclic cpds., including methods for synthesis thereof. WO 0001381 . |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| 14713 | benzenesulfonyl chloride | 98-09-9 | C6H5ClO2S | 详情 | 详情 | |
| (I) | 19639 | 4-fluorophenol | 371-41-5 | C6H5FO | 详情 | 详情 |
| (II) | 10146 | Epichlorohydrin; 2-(Chloromethyl)oxirane | 106-89-8 | C3H5ClO | 详情 | 详情 |
| (III) | 22150 | 2-[(4-fluorophenoxy)methyl]oxirane; 4-fluorophenyl 2-oxiranylmethyl ether | 18123-82-5 | C9H9FO2 | 详情 | 详情 |
| (IV) | 32985 | (2R)-3-(4-fluorophenoxy)-1,2-propanediol | C9H11FO3 | 详情 | 详情 | |
| (V) | 32986 | 4-fluorophenyl (2S)oxiranylmethyl ether; (2S)-2-[(4-fluorophenoxy)methyl]oxirane | 108648-25-5 | C9H9FO2 | 详情 | 详情 |
| (VI) | 32987 | (2S)-3-(4-fluorophenoxy)-2-hydroxypropyl 4-methylbenzenesulfonate | C16H17FO5S | 详情 | 详情 | |
| (VII) | 22150 | 2-[(4-fluorophenoxy)methyl]oxirane; 4-fluorophenyl 2-oxiranylmethyl ether | 18123-82-5 | C9H9FO2 | 详情 | 详情 |
| (VIII) | 10386 | Allyl(bromo)magnesium | 1730-25-2 | C3H5BrMg | 详情 | 详情 |
| (IX) | 32988 | (2R)-1-(4-fluorophenoxy)-5-hexen-2-ol | C12H15FO2 | 详情 | 详情 | |
| (X) | 32989 | (1R)-1-[(4-fluorophenoxy)methyl]-4-pentenyl benzenesulfonate | C18H19FO4S | 详情 | 详情 | |
| (XI) | 32990 | (1R)-1-[(4-fluorophenoxy)methyl]-4-oxobutyl benzenesulfonate | C17H17FO5S | 详情 | 详情 | |
| (XII) | 14182 | ethyl 2-(triphenyl-lambda(5)-phosphanylidene)acetate; (Carbethoxymethylene)triphenylphosphorane | 1099-45-2 | C22H21O2P | 详情 | 详情 |
| (XIII) | 32991 | ethyl (E,6R)-7-(4-fluorophenoxy)-6-[(phenylsulfonyl)oxy]-2-heptenoate | C21H23FO6S | 详情 | 详情 | |
| (XIV) | 32992 | (1R,4E)-1-[(4-fluorophenoxy)methyl]-6-hydroxy-4-hexenyl benzenesulfonate | C19H21FO5S | 详情 | 详情 | |
| (XV) | 32993 | (1R)-1-[(4-fluorophenoxy)methyl]-3-[(2R,3S)-3-(hydroxymethyl)oxiranyl]propyl benzenesulfonate | C19H21FO6S | 详情 | 详情 | |
| (XVI) | 32994 | (1R)-3-[(2R,3R)-3-(chloromethyl)oxiranyl]-1-[(4-fluorophenoxy)methyl]propyl benzenesulfonate | C19H20ClFO5S | 详情 | 详情 |
合成路线8
该中间体在本合成路线中的序号：(XVII)Hydrogenolysis of the benzyl ester of (XIII) over Pd/C gave peptide acid (XIV), which was converted to the mixed anhydride (XV) using isobutyl chloroformate and N-methylmorpholine. (Aminobutenyl)- dioxaborolane (XIX) was obtained by treatment of the (dichloromethyl)dioxaborolane (XVI) with allylmagnesium bromide (XVII), and subsequent displacement of the remaining chlorine atom with lithium bis(trimethylsilyl)amide. Condensation of anhydride (XV) with racemic aminoborolane (XIX) produced (XX) as a diastereomeric mixture. Finally, removal of the tert-butyl esters and hydrolysis of the dioxaborolane to the target boronic acid was effected with trifluoroacetic acid in CH2Cl2.
| 【1】 Attwood, M.R.; Campbell, A.D.; Bennett, J.M.; et al.; The design and synthersis of potent inhibitors of hepatitis C virus NS3-4A proteinase. Antivir Chem Chemother 1999, 10, 5, 259. |
| 【2】 Attwood, M.R.; Hurst, D.N.; Jones, P.S.; Kay, P.B.; Raynham, T.M.; Wilson, F.X. (F. Hoffmann-La Roche AG); Antiviral peptide derivs.. JP 2000508344; WO 9822496 . |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XIII) | 22263 | 1-benzyl 19-(tert-butyl) (2S,5S,8S,11S,14S)-14-[2-(tert-butoxy)-2-oxoethyl]-11-[3-(tert-butoxy)-3-oxopropyl]-5-(tert-butyl)-2-isobutyl-8-(2-methylbenzyl)-4,7,10,13,16-pentaoxo-3,6,9,12,15-pentaazanonadecane-1,19-dioate | C54H81N5O13 | 详情 | 详情 | |
| (XIV) | 22264 | (2S,5S,8S,11S,14S)-14-[2-(tert-butoxy)-2-oxoethyl]-11-[3-(tert-butoxy)-3-oxopropyl]-5-(tert-butyl)-2-isobutyl-21,21-dimethyl-8-(2-methylbenzyl)-4,7,10,13,16,19-hexaoxo-20-oxa-3,6,9,12,15-pentaazadocosan-1-oic acid | C47H75N5O13 | 详情 | 详情 | |
| (XV) | 22265 | 4-Tert-butoxysuccinyl-(4-O-tert-butyl)-L-aspartyl-(5-O-tert-butyl)-L-glutamyl-(2-methyl)-L-phenylalanyl-L-tert-leucyl-L-leucine isobutoxycarbonyl anhydride; 4-Tert-butoxysuccinyl-(4-O-tert-butyl)-L-aspartyl-(5-O-tert-butyl)-L-glutamyl-(2-methyl)-L-phenylalanyl-L-tert-leucyl-L-leucine isobutoxycarbonyl anhydride | C52H83N5O15 | 详情 | 详情 | |
| (XVI) | 22266 | 2-(dichloromethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | C7H13BCl2O2 | 详情 | 详情 | |
| (XVII) | 10386 | Allyl(bromo)magnesium | 1730-25-2 | C3H5BrMg | 详情 | 详情 |
| (XVIII) | 22272 | 2-(1-chloro-3-butenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | C10H18BClO2 | 详情 | 详情 | |
| (XIX) | 65180 | 1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3-butenylamine; 1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3-buten-1-amine | C10H20BNO2 | 详情 | 详情 | |
| (XX) | 22274 | tert-butyl (6S,9S,12S,15S,18S)-6-[2-(tert-butoxy)-2-oxoethyl]-9-[3-(tert-butoxy)-3-oxopropyl]-15-(tert-butyl)-18-isobutyl-12-(2-methylbenzyl)-4,7,10,13,16,19-hexaoxo-21-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5,8,11,14,17,20-hexaaza-23-tetracosen-1-oate | C57H93BN6O14 | 详情 | 详情 |
合成路线9
该中间体在本合成路线中的序号：(II)1) The reaction of undecanal (I) with vinylmagnesium bromide (II) in THF gives 1-tridecen-3-ol (III), which is condensed with propionic acid (IV) by means of triethyl orthoacetate in refluxing xylene yielding 4(E)-pentadecenoic acid ethyl ester (V). The reaction of (V) with AD-mix-beta and methanesulfonamide in tert-butanol affords (R,R)-5-(1-hydroxyundecyl)tetrahydrofuran-2-one (VI), which by reaction with p-nitrobenzoic acid and triphenylphosphine in benzene gives the corresponding ester (VII). The reaction of (VII) first with LiAlH4 in ether, followed by a treatment with acetone and p-toluenesulfonic acid yields the acetonide (VIII), which by oxidation of its primary alcohol with pyridinium chlorochromate (PCC) in dichloromethane affords the corresponding aldehyde (IX). The reaction of (IX) with vinylmagnesium bromide (II) in ether gives the allyl alcohol (X), which by condensation with proionic acid (IV) and triethyl orthoacetate yields (4E,8R,9S)-8,9-(isopropylidenedioxy)-4-nonadecenoic acid ethyl ester (XI), The reduction of (XI) with diisobutylaluminum hydride (DIBAL) in toluene affords the corresponding aldehyde (XII), which is condensed with triethyl phosphonoacetate (XIII) by means of NaH in toluene giving (2E,6E,10R,11S)-10,11-(isopropylidenedioxy)-heneicosa-2,6-dienoic acid ethyl ester (XIV).
| 【1】 Yazbak, A.; et al.; Total synthesis of uvaricin. J Org Chem 1998, 63, 17, 5863. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (I) | 20175 | undecanal | 112-44-7 | C11H22O | 详情 | 详情 |
| (II) | 10386 | Allyl(bromo)magnesium | 1730-25-2 | C3H5BrMg | 详情 | 详情 |
| (III) | 20177 | 1-tridecen-3-ol | C13H26O | 详情 | 详情 | |
| (IV) | 20178 | propionic acid | 79-09-4 | C3H6O2 | 详情 | 详情 |
| (V) | 20179 | ethyl (E)-4-pentadecenoate | C17H32O2 | 详情 | 详情 | |
| (VI) | 20180 | (5R)-5-[(1R)-1-hydroxyundecyl]dihydro-2(3H)-furanone | C15H28O3 | 详情 | 详情 | |
| (VII) | 20181 | (1R)-1-[(2S)-4-oxo-1,3-dioxolan-2-yl]undecyl 4-nitrobenzoate | C21H29NO7 | 详情 | 详情 | |
| (VIII) | 20182 | 3-[(4R,5S)-5-decyl-2,2-dimethyl-1,3-dioxolan-4-yl]-1-propanol | C18H36O3 | 详情 | 详情 | |
| (IX) | 20183 | 3-[(4R,5S)-5-decyl-2,2-dimethyl-1,3-dioxolan-4-yl]propanal | C18H34O3 | 详情 | 详情 | |
| (X) | 20184 | (3S)-5-[(4R,5S)-5-decyl-2,2-dimethyl-1,3-dioxolan-4-yl]-1-penten-3-ol | C20H38O3 | 详情 | 详情 | |
| (XI) | 20185 | ethyl (E)-7-[(4R,5S)-5-decyl-2,2-dimethyl-1,3-dioxolan-4-yl]-4-heptenoate | C24H44O4 | 详情 | 详情 | |
| (XII) | 20186 | (E)-7-[(4R,5S)-5-decyl-2,2-dimethyl-1,3-dioxolan-4-yl]-4-heptenal | C22H40O3 | 详情 | 详情 | |
| (XIII) | 10019 | Ethyl 2-(diethoxyphosphoryl)acetate; Triethyl phosphonoacetate | 867-13-0 | C8H17O5P | 详情 | 详情 |
| (XIV) | 20188 | ethyl (2E,6E)-9-[(4R,5S)-5-decyl-2,2-dimethyl-1,3-dioxolan-4-yl]-2,6-nonadienoate | C26H46O4 | 详情 | 详情 |
合成路线10
该中间体在本合成路线中的序号：(II)Synthesis of the acetylenic dihydropyran intermediate (VII): The reaction of the chiral oxazolinone (I) with allylmagnesium bromide (II) by means of CuBr, BF3/Et2O and Mg(OMe)2, followed by ozonolysis with O3 in dichloromethane gives the aldehyde (III), which is condensed with the enol ether (IV) by means of a chiral Cr catalist to yield the dihydropyranone(V). The reduction of (V) with NaBH4 and CeCl3, followed by acylation with Ac2O affords the acetoxydihydropyran derivative (VI). Which is finally condensed with the allenic tributyl tin compound (VII) and trimethylsilylmethyl magnesium chloride in THF to provide the target acetylenic dihydropyran intermediate (VIII).
| 【1】 Williams, D.R.; et al.; Synthesis of (-)-laulimalide: An agent for microtubule stabilization. Tetrahedron Lett 2002, 43, 27, 4841. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (I) | 62935 | (4R)-3-[(E)-2-butenoyl]-4-phenyl-1,3-oxazolidin-2-one | C13H13NO3 | 详情 | 详情 | |
| (II) | 10386 | Allyl(bromo)magnesium | 1730-25-2 | C3H5BrMg | 详情 | 详情 |
| (III) | 62936 | Methyl (3R)-3-methyl-5-oxopentanoate | C7H12O3 | 详情 | 详情 | |
| (IV) | 62937 | {[(E)-3-methoxy-1-methylene-2-propenyl]oxy}(trimethyl)silane; (E)-3-methoxy-1-methylene-2-propenyl trimethylsilyl ether | C8H16O2Si | 详情 | 详情 | |
| (V) | 62938 | methyl (3R)-3-methyl-4-[(2R)-4-oxo-3,4-dihydro-2H-pyran-2-yl]butanoate | C11H16O4 | 详情 | 详情 | |
| (VI) | 62939 | methyl (3R)-4-[(2R,4S)-4-(acetyloxy)-3,4-dihydro-2H-pyran-2-yl]-3-methylbutanoate | C13H20O5 | 详情 | 详情 | |
| (VII) | 62940 | 2-[1,1'-biphenyl]-4-ylethyl 2-(tributylstannyl)-2,3-butadienyl ether; 4-(2-{[2-(tributylstannyl)-2,3-butadienyl]oxy}ethyl)-1,1'-biphenyl | C30H44OSn | 详情 | 详情 | |
| (VIII) | 62941 | 2-[1,1'-biphenyl]-4-ylethyl 4-((2R,6R)-6-{(2S)-2-methyl-4-[(trimethylsilyl)methyl]-4-pentenyl}-5,6-dihydro-2H-pyran-2-yl)-2-butynyl ether; 4-(2-{[4-((2R,6R)-6-{(2S)-2-methyl-4-[(trimethylsilyl)methyl]-4-pentenyl}-5,6-dihydro-2H-pyran-2-yl)-2-butynyl]oxy}ethyl)-1,1'-biphenyl | C33H44O2Si | 详情 | 详情 |
合成路线11
该中间体在本合成路线中的序号：(A)The Grignard reaction of dibenzo[a,d]cyclohepta-1,4,6-triene-5-one (I) with allyl magnesium bromide (A) in ethyl ether gives 5-hydroxy-5-allyldibenzo[a,d]cyclohepta-1,4,6-triene (II), which is dehydrated with acetic anhydride and acetyl chloride at 90 C yielding 5-propenylidenedibenzo[a,d]cyclohepta-1,4,6-triene (III). Finally, this compound is treated with phenylmagnesium bromide and dimethylamine (B) at 80 C.
| 【1】 Roberts, P.J.; Castañer, J.; Cyclobenzaprine. Drugs Fut 1977, 2, 5, 299. |
| 【2】 Schmitt, G. (F. Hoffmann-La Roche AG); A process for the manufacture of tricyclic amines. BE 0636000; CH 385191; DE 1468006; FR 1366413; GB 990105 . |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (A) | 10386 | Allyl(bromo)magnesium | 1730-25-2 | C3H5BrMg | 详情 | 详情 |
| (B) | 19443 | N-methylmethanamine; N,N-dimethylamine | 124-40-3 | C2H7N | 详情 | 详情 |
| (I) | 29151 | 5H-dibenzo[a,d]cyclohepten-5-one; Dibenzosuberenone | 2222-33-5 | C15H10O | 详情 | 详情 |
| (II) | 40125 | 5-allyl-5H-dibenzo[a,d]cyclohepten-5-ol | C18H16O | 详情 | 详情 | |
| (III) | 40126 | 5-(2-propenylidene)-5H-dibenzo[a,d]cycloheptene | C18H14 | 详情 | 详情 |