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【结 构 式】 
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【分子编号】27301 【品名】methylene(triphenyl)phosphorane 【CA登记号】 |
【 分 子 式 】C19H17P 【 分 子 量 】276.317742 【元素组成】C 82.59% H 6.2% P 11.21% |
合成路线1
该中间体在本合成路线中的序号：(II)By a Wittig condensation of 17-cyclobutylmethyl-3-hydroxy-8beta-methyl morphinan-6-one (I) with triphenylmethylenephosphorane in DMSO.
| 【1】 Kotick, M.P.; Polazzi, J.O. (Bayer Corp.); 17-Cyclobutylmethyl-3-hydroxy-beta-methyl-6-methylene morphinane, and methods of treating pain with them. CA 1128508; EP 0027925; ES 8107222; US 4259329 . |
| 【2】 Serradell, M.N.; Blancafort, P.; Castaner, J.; TR-5379. Drugs Fut 1982, 7, 1, 40. |
合成路线2
该中间体在本合成路线中的序号：(IV)The formylation of the beta-ionone (I) with methyl formate and NaOMe gives the enol (II), which by reaction with methanol and H2SO4 yields the dimethylacetal (III). The reaction of (III) with methylenetriphenylphosphorane (IV) affords the methylene compound (V), which is treated with formic acid to provide the aldehyde (VI). The condensation of (VI) with isopropylidenemalonic acid dimethyl ester (VII) by means of NaOH gives the polyenic malonic acid (VIII) as a mixture of isomers that is separated by crystallization in ethyl ether to yield the desired all-trans-isomer (IX). Finally, this malonic acid is selectively monodecarboxylated by means of refluxing 2,6-dimethylpyridine to afford the target (E,E,E,Z)-isomer.
| 【1】 Valia, A.; et al.; Stereoselective synthesis of 13 E retinoic and 13 Z retinoic acids via a new intermediate compound, C-15 beta-methylenealdehyde. Tetrahedron 2000, 56, 37, 7211. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (VIIIa),(IX) | 49672 | 2-[(2E,4E,6E)-1,5-dimethyl-7-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4,6-heptatrienylidene]malonic acid | C21H28O4 | 详情 | 详情 | |
| (VIIb) | 49673 | 2-[(2E,4Z,6E)-1,5-dimethyl-7-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2,4,6-heptatrienylidene]malonic acid | C21H28O4 | 详情 | 详情 | |
| (I) | 39584 | (E)-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-3-buten-2-one | 14901-07-6 | C13H20O | 详情 | 详情 |
| (II) | 49667 | (1E,4E)-1-hydroxy-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1,4-pentadien-3-one | C14H20O2 | 详情 | 详情 | |
| (III) | 49668 | (E)-5,5-dimethoxy-1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1-penten-3-one | C16H26O3 | 详情 | 详情 | |
| (IV) | 27301 | methylene(triphenyl)phosphorane | C19H17P | 详情 | 详情 | |
| (V) | 49669 | (E)-1-methoxy-3-methylene-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-4-pentenyl methyl ether; 2-[(1E)-3-(2,2-dimethoxyethyl)-1,3-butadienyl]-1,3,3-trimethyl-1-cyclohexene | C17H28O2 | 详情 | 详情 | |
| (VI) | 49670 | (E)-3-methylene-5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-4-pentenal | C15H22O | 详情 | 详情 | |
| (VII) | 49671 | dimethyl 2-(1-methylethylidene)malonate | 22035-53-6 | C8H12O4 | 详情 | 详情 |
合成路线3
该中间体在本合成路线中的序号：The reaction of protected pyrrolidone (VIII) with LHMDS and CO2 affords the corresponding pyrrolidonecarboxylic acid (IX), which is reduced at the ketonic oxygen with NaBH4 providing the hydroxyacid (X). The condensation of the previously obtained amino acid (VII) with the acid (X) by means of oxalyl chloride and triethylamine affords amide (XI), which is condensed with vinyltributylstannane (XII) by means of Pd(PPh3)4 to give the butaiene derivative (XIII). The spontaneous Diels-Alder cyclization of (XIII) yields the tricyclic compound (XIV), which is oxidized with CrO3 to the dione (XV). The deprotection of the hydroxyl groups of (XV), their reaction with oxalyl chloride and with methylenetriphenylphosphorane provides compound (XVI) with two terminal reactive double bonds. The reduction of (XVI) with DIBAL, followed by oxidation with Dess Martin periodinane (DMP) affords the corresponding aldehyde (XVII).
| 【1】 Martin, S.F.; et al.; Enantioselective total synthesis of ircinal A and related manzamine alkaloids. J Am Chem Soc 1999, 121, 4, 866. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| 27301 | methylene(triphenyl)phosphorane | C19H17P | 详情 | 详情 | ||
| (VII) | 24915 | methyl (Z)-2-bromo-5-[(5-[[tert-butyl(diphenyl)silyl]oxy]pentyl)amino]-2-pentenoate | C27H38BrNO3Si | 详情 | 详情 | |
| (VIII) | 24916 | tert-butyl (2R)-2-([[tert-butyl(diphenyl)silyl]oxy]methyl)-5-oxo-1-pyrrolidinecarboxylate | C26H35NO4Si | 详情 | 详情 | |
| (IX) | 24917 | (5R)-1-(tert-butoxycarbonyl)-5-([[tert-butyl(diphenyl)silyl]oxy]methyl)-2-oxo-3-pyrrolidinecarboxylate | C27H34NO6Si | 详情 | 详情 | |
| (X) | 24918 | (5R)-1-(tert-butoxycarbonyl)-5-([[tert-butyl(diphenyl)silyl]oxy]methyl)-2-hydroxy-3-pyrrolidinecarboxylate | C27H36NO6Si | 详情 | 详情 | |
| (XI) | 24919 | tert-butyl (2R)-4-[[[(E)-4-bromo-5-methoxy-5-oxo-3-pentenyl](5-[[tert-butyl(diphenyl)silyl]oxy]pentyl)amino]carbonyl]-2-([[tert-butyl(diphenyl)silyl]oxy]methyl)-2,3-dihydro-1H-pyrrole-1-carboxylate | C54H71BrN2O7Si2 | 详情 | 详情 | |
| (XII) | 24920 | tributyl(vinyl)stannane；Tributylvinylstannane;Vinyltributylstannane | 7486-35-3 | C14H30Sn | 详情 | 详情 |
| (XIII) | 24921 | tert-butyl (2R)-2-([[tert-butyl(diphenyl)silyl]oxy]methyl)-4-([(5-[[tert-butyl(diphenyl)silyl]oxy]pentyl)[(3Z)-4-(methoxycarbonyl)-3,5-hexadienyl]amino]carbonyl)-2,3-dihydro-1H-pyrrole-1-carboxylate | C56H74N2O7Si2 | 详情 | 详情 | |
| (XIV) | 24922 | 1-(tert-butyl) 8-methyl (2R,3aS,7aR,10aS)-2-([[tert-butyl(diphenyl)silyl]oxy]methyl)-5-(5-[[tert-butyl(diphenyl)silyl]oxy]pentyl)-4-oxo-2,3,5,6,7,7a,10,10a-octahydropyrrolo[2,3-i]isoquinoline-1,8(4H)-dicarboxylate | C56H74N2O7Si2 | 详情 | 详情 | |
| (XV) | 24923 | 1-(tert-butyl) 8-methyl (2R,3aS,7aR,10aR)-2-([[tert-butyl(diphenyl)silyl]oxy]methyl)-5-(5-[[tert-butyl(diphenyl)silyl]oxy]pentyl)-4,10-dioxo-2,3,5,6,7,7a,10,10a-octahydropyrrolo[2,3-i]isoquinoline-1,8(4H)-dicarboxylate | C56H72N2O8Si2 | 详情 | 详情 | |
| (XVI) | 24924 | 1-(tert-butyl) 8-methyl (2R,3aS,7aR,10aR)-5-(5-hexenyl)-4,10-dioxo-2-vinyl-2,3,5,6,7,7a,10,10a-octahydropyrrolo[2,3-i]isoquinoline-1,8(4H)-dicarboxylate | C26H36N2O6 | 详情 | 详情 | |
| (XVII) | 24925 | tert-butyl (2R,3aR,7aR,10aR)-8-formyl-5-(5-hexenyl)-10-oxo-2-vinyl-2,3,5,6,7,7a,10,10a-octahydropyrrolo[2,3-i]isoquinoline-1(4H)-carboxylate | C25H36N2O4 | 详情 | 详情 |
合成路线4
该中间体在本合成路线中的序号：(IV)The Friedel Craft condensation of 1,3-difluorobenzene (I) with succinic anhydride (II) gives the 4-oxobutyric acid (III); which by a Wittig reaction with methylene triphenylphosphorane (IV) yields the 4-pentenoic acid (V). The condensation of (V) with the chiral auxiliary, 4(R)-benyzloxazolidin-2-one (VI) by means of pivaloyl chloride and BuLi affords the chiral imide (VII), which is submitted to a diastereoselective hydroxymethylation with trioxane and TiCl4 in THF to provide the hydroxymethyl adduct (VIII). The direct iodocyclization of (VIII) by means of I2 and pyridine in acetonitrile gives the chiral cis-tetrahydrofuran derivative (IX). The reductive cleavage of the chiral auxiliary of (IX) by means of LiBH4 in THF yields the iodoalcohol (X)???(X)a, which is condensed with 1,2,4-triazole sodium salt (XI) to afford the adduct (XII). Finally, this compound is treated with Ts-Cl and pyridine to afford the target intermediate tosylate (XIII) (see scheme no. 20027601a, intermediate no. (II)).
| 【1】 Saksena, A.K.; Girijavallabhan, V.M.; Wang, H.Y.; Liu, Y.T.; Pike, R.E.; Ganguly, A.K.; Concise asymmetric routes to 2,2,4-trisubstituted tetrahydrofurans via chiral titanium imide enolates: Key intermediates towards synthesis of highly active azole antifungals Sch 51048 and Sch 56592. Tetrahedron Lett 1996, 37, 32, 5657. |
| 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) | 13095 | m-Difluorobenzene; 1,3-Difluorobenzene | 372-18-9 | C6H4F2 | 详情 | 详情 |
| (II) | 11291 | Dihydro-2,5-furandione; Succinic anhydride | 108-30-5 | C4H4O3 | 详情 | 详情 |
| (III) | 17089 | 4-(2,4-difluorophenyl)-4-oxobutyric acid | 110931-77-6 | C10H8F2O3 | 详情 | 详情 |
| (IV) | 27301 | methylene(triphenyl)phosphorane | C19H17P | 详情 | 详情 | |
| (V) | 17090 | 4-(2,4-difluorophenyl)-4-pentenoic acid | C11H10F2O2 | 详情 | 详情 | |
| (VI) | 25351 | (4R)-4-benzyl-1,3-oxazolidin-2-one; (R)-(+)-4-benzyl-2-oxazolidinone | 102029-44-7 | C10H11NO2 | 详情 | 详情 |
| (VII) | 58310 | (4R)-4-benzyl-3-[4-(2,4-difluorophenyl)-4-pentenoyl]-1,3-oxazolidin-2-one | C21H19F2NO3 | 详情 | 详情 | |
| (VIII) | 58311 | (4R)-4-benzyl-3-[(2S)-4-(2,4-difluorophenyl)-2-(hydroxymethyl)-4-pentenoyl]-1,3-oxazolidin-2-one | C22H21F2NO4 | 详情 | 详情 | |
| (IX) | 58312 | (4R)-4-benzyl-3-{[(3S,5R)-5-(2,4-difluorophenyl)-5-(iodomethyl)tetrahydro-3-furanyl]carbonyl}-1,3-oxazolidin-2-one | C22H20F2INO4 | 详情 | 详情 | |
| (X) | 17096 | [(3R,5R)-5-(2,4-difluorophenyl)-5-(iodomethyl)tetrahydro-3-furanyl]methanol | C12H13F2IO2 | 详情 | 详情 | |
| (XI) | 16341 | 1H-1,2,4-triazol-1-ylsodium | C2H2N3Na | 详情 | 详情 | |
| (XII) | 16343 | [(3R,5R)-5-(2,4-difluorophenyl)-5-(1H-1,2,4-triazol-1-ylmethyl)tetrahydro-3-furanyl]methanol | C14H15F2N3O2 | 详情 | 详情 | |
| (XIII) | 16311 | [(3S,5R)-5-(2,4-difluorophenyl)-5-(1H-1,2,4-triazol-1-ylmethyl)tetrahydro-3-furanyl]methyl 4-methylbenzenesulfonate | C21H21F2N3O4S | 详情 | 详情 |
合成路线5
该中间体在本合成路线中的序号：(XVI)The intermediate phosphonium bromide (XVII) is obtained as follows: The reaction of the glucoside (I) with Me2CuLi in THF gives the methyl derivative (II), which is converted into the unsaturated pyranoside (III). The reductive deoxygenation of (III) with Pd(OAc)2 and NaBH4 affords the acetate (IV), which is treated with NaOMe in methanol to afford the carbinol (V). The oxidation of (V) with oxalyl chloride in DMSO provides the carbaldehyde (VI), which is treated with Me-Mg-Br in THF to give the secondary alcohol (VII). The oxidation of (VII) with oxalyl chloride in DMSO yields the ketone (VIII), which is condensed with the phosphonate (IX) (obtained by reaction of 4-(chloromethyl)-2-methylthiazole (X) with triethyl phosphite (XI) at 165 C) by means of tBu-OK in THF to afford the vinyl-dihydropyran (XII). The opening of the dihydropyran ring of (XII) by means of HOAc in THF/water, followed by reduction of the intermediate aldehyde, provides the unsaturated diol (XIII). The regioselective bromination of (XIII) with CBr4 and PPh3 in acetonitrile gives the bromo derivative (XIV), which is silylated with Tbdms-OTf to yield the silyl ether derivative (XV). Finally, this compound is condensed with methylenetriphenylphosphorane (XVI) in THF to afford the target intermediate, the phosphonium bromide (XVII).
| 【1】 Potier, P.; Ermolenko, M.S.; Synthesis of epothilones B and D from D-glucose. Tetrahedron Lett 2002, 43, 16, 2895. |
| 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) | 54335 | (1aR,2S,3aR,6R,7aS,7bS)-2-methoxy-6-phenylhexahydrooxireno[2',3':4,5]pyrano[3,2-d][1,3]dioxine; (1aR,2S,3aR,6R,7aS,7bS)-6-phenylhexahydrooxireno[2',3':4,5]pyrano[3,2-d][1,3]dioxin-2-yl methyl ether | n/a | C14H16O5 | 详情 | 详情 |
| (II) | 54336 | (2R,4aR,6S,7S,8S,8aS)-6-methoxy-7-methyl-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-8-ol | n/a | C15H20O5 | 详情 | 详情 |
| (III) | 54337 | [(2R,3S,6S)-3-(acetyloxy)-6-methoxy-5-methyl-3,6-dihydro-2H-pyran-2-yl]methyl acetate | n/a | C12H18O6 | 详情 | 详情 |
| (IV) | 54338 | [(2S,6S)-6-methoxy-5-methyl-3,6-dihydro-2H-pyran-2-yl]methyl acetate | n/a | C10H16O4 | 详情 | 详情 |
| (V) | 54339 | [(2S,6S)-6-methoxy-5-methyl-3,6-dihydro-2H-pyran-2-yl]methanol | n/a | C8H14O3 | 详情 | 详情 |
| (VI) | 54340 | (2S,6S)-6-methoxy-5-methyl-3,6-dihydro-2H-pyran-2-carbaldehyde | n/a | C8H12O3 | 详情 | 详情 |
| (VII) | 54341 | (1R)-1-[(2S,6S)-6-methoxy-5-methyl-3,6-dihydro-2H-pyran-2-yl]-1-ethanol | n/a | C9H16O3 | 详情 | 详情 |
| (VIII) | 54342 | 1-[(2S,6S)-6-methoxy-5-methyl-3,6-dihydro-2H-pyran-2-yl]-1-ethanone | n/a | C9H14O3 | 详情 | 详情 |
| (IX) | 44442 | diethyl (2-methyl-1,3-thiazol-4-yl)methylphosphonate | C9H16NO3PS | 详情 | 详情 | |
| (X) | 40819 | 4-(chloromethyl)-2-methyl-1,3-thiazole | C5H6ClNS | 详情 | 详情 | |
| (XII) | 54343 | 4-{(E)-2-[(2S,6S)-6-methoxy-5-methyl-3,6-dihydro-2H-pyran-2-yl]-1-propenyl}-2-methyl-1,3-thiazole; methyl (2S,6S)-3-methyl-6-[(E)-1-methyl-2-(2-methyl-1,3-thiazol-4-yl)ethenyl]-5,6-dihydro-2H-pyran-2-yl ether | n/a | C14H19NO2S | 详情 | 详情 |
| (XIII) | 54344 | (2Z,5S,6E)-2,6-dimethyl-7-(2-methyl-1,3-thiazol-4-yl)-2,6-heptadiene-1,5-diol | n/a | C13H19NO2S | 详情 | 详情 |
| (XIV) | 54345 | (1E,3S,5Z)-7-bromo-2,6-dimethyl-1-(2-methyl-1,3-thiazol-4-yl)-1,5-heptadien-3-ol | n/a | C13H18BrNOS | 详情 | 详情 |
| (XV) | 46147 | 4-((1E,3S,5Z)-7-bromo-3-[[tert-butyl(dimethyl)silyl]oxy]-2,6-dimethyl-1,5-heptadienyl)-2-methyl-1,3-thiazole; (1S,3Z)-5-bromo-4-methyl-1-[(E)-1-methyl-2-(2-methyl-1,3-thiazol-4-yl)ethenyl]-3-pentenyl tert-butyl(dimethyl)silyl ether | C19H32BrNOSSi | 详情 | 详情 | |
| (XVI) | 27301 | methylene(triphenyl)phosphorane | C19H17P | 详情 | 详情 | |
| (XVII) | 46148 | [(3Z,6S,7E)-6-[[tert-butyl(dimethyl)silyl]oxy]-3,7-dimethyl-8-(2-methyl-1,3-thiazol-4-yl)-3,7-octadienyl](triphenyl)phosphonium bromide | C38H49BrNOPSSi | 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 reaction of 3,5-dihydroxybenzaldehyde (I) with Tbdms-Cl gives the disilylated aldehyde (II), which by a Wittig condensation with methylenetriphenylphosphorane (III) yields the 3,5-dihydroxystyrene (IV). The reaction of (IV) with acetic anhydride and pyridine affords 3,5-diacetoxystyrene (V), which was submitted to a Heck condensation with 4-acetoxyiodobenzene (VI) by means of Pd(OAc)2 and PPh3 in hot acetonitrile to provide 3,4',5-triacetopxy-(E)-stilbene (VII). Finally, this compound is deacetylated by means of NaOMe in THF/methanol to furnish the target resveratrol.
| 【1】 Guiso, M.; et al.; A new efficient resveratrol synthesis. Tetrahedron Lett 2002, 43, 4, 597. |
| 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) | 52215 | 3,5-Dihydroxybenzaldehyde | C7H6O3 | 详情 | 详情 | |
| (II) | 52216 | 3,5-bis{[tert-butyl(dimethyl)silyl]oxy}benzaldehyde | C19H34O3Si2 | 详情 | 详情 | |
| (III) | 27301 | methylene(triphenyl)phosphorane | C19H17P | 详情 | 详情 | |
| (IV) | 52217 | 5-vinyl-1,3-benzenediol | C8H8O2 | 详情 | 详情 | |
| (V) | 52218 | 3-(acetyloxy)-5-vinylphenyl acetate | C12H12O4 | 详情 | 详情 | |
| (VI) | 52219 | 4-iodophenyl acetate | C8H7IO2 | 详情 | 详情 | |
| (VII) | 52220 | 3-(acetyloxy)-5-{(E)-2-[4-(acetyloxy)phenyl]ethenyl}phenyl acetate | C20H18O6 | 详情 | 详情 |
合成路线7
该中间体在本合成路线中的序号：The preparation of the precursor amino acids is shown in Schemes 1-4. Ozonolysis of (R)-citronellol (I), followed by Wittig reaction of the resulting aldehyde (II) with methylene triphenylphosphorane gave heptenol (III). Subsequent hydrogenation of (III) over Pd/C provided the saturated alcohol (IV), which was oxidized to the corresponding aldehyde (V) by treatment with Dess-Martin reagent. Asymmetric Strecker reaction in (V) utilizing (R)-phenylglycinol (VI) and trimethylsilyl cyanide afforded a diastereomeric mixture of aminonitriles (VII). After oxidative cleavage of (VII) with lead tetraacetate, the free (2S)-amine (VIII) was separated from its minor diastereomer by column chromatography. Acid hydrolysis of the nitrile group of (VIII) gave 5-propyl-L-leucine (IX), which was protected as the tert-butyl carbamate (X) with Boc2O.
| 【1】 Boger, D.L.; et al.; Total synthesis of HUN-7293. J Am Chem Soc 1999, 121, 26, 6197. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| 27301 | methylene(triphenyl)phosphorane | C19H17P | 详情 | 详情 | ||
| (A) | 18845 | Dess-Martin periodinane; 1,1,1-Triacetoxy-1,2-benziodoxol-3(1H)-one | 87413-09-0 | C13H13IO8 | 详情 | 详情 |
| (I) | 26264 | (3R)-3,7-dimethyl-6-octen-1-ol | 1117-61-9 | C10H20O | 详情 | 详情 |
| (II) | 26265 | (4R)-6-hydroxy-4-methylhexanal | C7H14O2 | 详情 | 详情 | |
| (III) | 26266 | (3R)-3-methyl-6-hepten-1-ol | C8H16O | 详情 | 详情 | |
| (IV) | 26267 | (3R)-3-methyl-1-heptanol | C8H18O | 详情 | 详情 | |
| (V) | 26268 | (3R)-3-methylheptanal | C8H16O | 详情 | 详情 | |
| (VI) | 14376 | (2R)-2-amino-2-phenyl-1-ethanol; (R)-(-)-2-phenylglycinol; (R)-2-amino-2-phenyl-1-ethanol | 56613-80-0 | C8H11NO | 详情 | 详情 |
| (VII) | 26269 | (4R)-2-[[(1R)-2-hydroxy-1-phenylethyl]amino]-4-methyloctanenitrile | C17H26N2O | 详情 | 详情 | |
| (VIII) | 26270 | (2S,4R)-2-amino-4-methyloctanenitrile | C9H18N2 | 详情 | 详情 | |
| (IX) | 26271 | (2S,4R)-2-amino-4-methyloctanoic acid | C9H19NO2 | 详情 | 详情 | |
| (X) | 26272 | (2S,4R)-2-[(tert-butoxycarbonyl)amino]-4-methyloctanoic acid | C14H27NO4 | 详情 | 详情 |
合成路线8
该中间体在本合成路线中的序号：(XVI)The intermediate phosphonium bromide (XVII) is obtained as follows: The reaction of the glucoside (I) with Me2CuLi in THF gives the methyl derivative (II), which is converted into the unsaturated pyranoside (III). The reductive deoxygenation of (III) with Pd(OAc)2 and NaBH4 affords the acetate (IV), which is treated with NaOMe in methanol to afford the carbinol (V). The oxidation of (V) with oxalyl chloride in DMSO provides the carbaldehyde (VI), which is treated with Me-Mg-Br in THF to give the secondary alcohol (VII). The oxidation of (VII) with oxalyl chloride in DMSO yields the ketone (VIII), which is condensed with the phosphonate (IX) (obtained by reaction of 4-(chloromethyl)-2-methylthiazole (X) with triethyl phosphite (XI) at 165 C) by means of tBu-OK in THF to afford the vinyl-dihydropyran (XII). The opening of the dihydropyran ring of (XII) by means of AcOH in THF/water, followed by reduction of the intermediate aldehyde, provides the unsaturated diol (XIII). The regioselective bromination of (XIII) with CBr4 and PPh3 in acetonitrile gives the bromo derivative (XIV), which is silylated with Tbdms-OTf to yield the silyl ether derivative (XV). Finally, this compound is condensed with methylenetriphenylphosphorane (XVI) in THF to afford the target intermediate, the phosphonium bromide (XVII).
| 【1】 Potier, P.; Ermolenko, M.S.; Synthesis of epothilones B and D from D-glucose. Tetrahedron Lett 2002, 43, 16, 2895. |
| 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) | 54335 | (1aR,2S,3aR,6R,7aS,7bS)-2-methoxy-6-phenylhexahydrooxireno[2',3':4,5]pyrano[3,2-d][1,3]dioxine; (1aR,2S,3aR,6R,7aS,7bS)-6-phenylhexahydrooxireno[2',3':4,5]pyrano[3,2-d][1,3]dioxin-2-yl methyl ether | n/a | C14H16O5 | 详情 | 详情 |
| (II) | 54336 | (2R,4aR,6S,7S,8S,8aS)-6-methoxy-7-methyl-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-8-ol | n/a | C15H20O5 | 详情 | 详情 |
| (III) | 54337 | [(2R,3S,6S)-3-(acetyloxy)-6-methoxy-5-methyl-3,6-dihydro-2H-pyran-2-yl]methyl acetate | n/a | C12H18O6 | 详情 | 详情 |
| (IV) | 54338 | [(2S,6S)-6-methoxy-5-methyl-3,6-dihydro-2H-pyran-2-yl]methyl acetate | n/a | C10H16O4 | 详情 | 详情 |
| (V) | 54339 | [(2S,6S)-6-methoxy-5-methyl-3,6-dihydro-2H-pyran-2-yl]methanol | n/a | C8H14O3 | 详情 | 详情 |
| (VI) | 54340 | (2S,6S)-6-methoxy-5-methyl-3,6-dihydro-2H-pyran-2-carbaldehyde | n/a | C8H12O3 | 详情 | 详情 |
| (VII) | 54341 | (1R)-1-[(2S,6S)-6-methoxy-5-methyl-3,6-dihydro-2H-pyran-2-yl]-1-ethanol | n/a | C9H16O3 | 详情 | 详情 |
| (VIII) | 54342 | 1-[(2S,6S)-6-methoxy-5-methyl-3,6-dihydro-2H-pyran-2-yl]-1-ethanone | n/a | C9H14O3 | 详情 | 详情 |
| (IX) | 44442 | diethyl (2-methyl-1,3-thiazol-4-yl)methylphosphonate | C9H16NO3PS | 详情 | 详情 | |
| (X) | 40819 | 4-(chloromethyl)-2-methyl-1,3-thiazole | C5H6ClNS | 详情 | 详情 | |
| (XII) | 54343 | 4-{(E)-2-[(2S,6S)-6-methoxy-5-methyl-3,6-dihydro-2H-pyran-2-yl]-1-propenyl}-2-methyl-1,3-thiazole; methyl (2S,6S)-3-methyl-6-[(E)-1-methyl-2-(2-methyl-1,3-thiazol-4-yl)ethenyl]-5,6-dihydro-2H-pyran-2-yl ether | n/a | C14H19NO2S | 详情 | 详情 |
| (XIII) | 54344 | (2Z,5S,6E)-2,6-dimethyl-7-(2-methyl-1,3-thiazol-4-yl)-2,6-heptadiene-1,5-diol | n/a | C13H19NO2S | 详情 | 详情 |
| (XIV) | 54345 | (1E,3S,5Z)-7-bromo-2,6-dimethyl-1-(2-methyl-1,3-thiazol-4-yl)-1,5-heptadien-3-ol | n/a | C13H18BrNOS | 详情 | 详情 |
| (XV) | 46147 | 4-((1E,3S,5Z)-7-bromo-3-[[tert-butyl(dimethyl)silyl]oxy]-2,6-dimethyl-1,5-heptadienyl)-2-methyl-1,3-thiazole; (1S,3Z)-5-bromo-4-methyl-1-[(E)-1-methyl-2-(2-methyl-1,3-thiazol-4-yl)ethenyl]-3-pentenyl tert-butyl(dimethyl)silyl ether | C19H32BrNOSSi | 详情 | 详情 | |
| (XVI) | 27301 | methylene(triphenyl)phosphorane | C19H17P | 详情 | 详情 | |
| (XVII) | 46148 | [(3Z,6S,7E)-6-[[tert-butyl(dimethyl)silyl]oxy]-3,7-dimethyl-8-(2-methyl-1,3-thiazol-4-yl)-3,7-octadienyl](triphenyl)phosphonium bromide | C38H49BrNOPSSi | 详情 | 详情 |
合成路线9
该中间体在本合成路线中的序号：(XVIII)A stereoselective synthesis of beta-elemene has been reported: Reaction of 2-allylpropane-1,3-diol (I) with tosyl chloride and pyridine gives the ditosylate (II), which is treated with NaCN in refluxing DMF to yield the dinitrile (III). The methanolysis of (III) with TsOH and refluxing methanol affords the dicarboxylic acid (IV), which is reduced with LiAlH4 in THF providing 3-allyl-1,5-pentanediol (V). The reaction of (V) with CBr4 and PPh3 in dichloromethane gives the dibromide (VI), which is ozonolyzed with ozone and PPh3 in dichloromethane to yield the aldehyde (VII). Condensation of (VII) with the phosphorane (VIII) in dichloromethane affords the unsaturated ester (IX), which is reduced with DIBAL in toluene to afford alcohol (X). Condensation of (X) with triethyl orthopropionate (XI) in refluxing phenol/toluene gives the anti-dibromoester (XII), along with some syn-isomer that is easily separated. Cyclization of (XII) with LDA in THF yields the cyclohexanecarboxylate (XIII), which is treated with t-BuOK in THF to afford the divinylcylohexanecarboxylate (XIV). Reduction of (XV) with DIBAL in toluene provides the carbinol (XV), which is treated with CuCl, PdCl2 and O2 in DMF/water giving the acetyl derivative (XVI). Oxidation of (XVI) with PCC and AcONa in dichloromethane gives keto-aldehyde (XVII), which is finally submitted to a double Wittig methylenation with methylenetriphenylphosphorane (XVIII) in THF.
| 【1】 Lee, J.; Kim, S.; Kim, D.; Chang, J.; Stereoselective synthesis of (±)-beta-elemene by a doubly diastereodifferentiating internal alkylation: A remarkable difference in the rate of enolization between syn and anti esters. Tetrahedron 2001, 57, 7, 1247. |
| 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) | 45745 | 2-allyl-1,3-propanediol | C6H12O2 | 详情 | 详情 | |
| (II) | 45746 | 2-([[(4-methylphenyl)sulfonyl]oxy]methyl)-4-pentenyl 4-methylbenzenesulfonate | C20H24O6S2 | 详情 | 详情 | |
| (III) | 45747 | 3-allylpentanedinitrile | C8H10N2 | 详情 | 详情 | |
| (IV) | 45748 | dimethyl 3-allylpentanedioate | C10H16O4 | 详情 | 详情 | |
| (V) | 45749 | 3-allyl-1,5-pentanediol | C8H16O2 | 详情 | 详情 | |
| (VI) | 45750 | 6-bromo-4-(2-bromoethyl)-1-hexene | C8H14Br2 | 详情 | 详情 | |
| (VII) | 45751 | 5-bromo-3-(2-bromoethyl)pentanal | C7H12Br2O | 详情 | 详情 | |
| (VIII) | 37071 | ethyl 2-(triphenylphosphoranylidene)propanoate | 5717-37-3 | C23H23O2P | 详情 | 详情 |
| (IX) | 45752 | ethyl (E)-7-bromo-5-(2-bromoethyl)-2-methyl-2-heptenoate | C12H20Br2O2 | 详情 | 详情 | |
| (X) | 45753 | (E)-7-bromo-5-(2-bromoethyl)-2-methyl-2-hepten-1-ol | C10H18Br2O | 详情 | 详情 | |
| (XI) | 10395 | 1,1,1-Triethoxypropane; 1,1-Diethoxypropyl ethyl ether; Triethyl orthopropionate | 115-80-0 | C9H20O3 | 详情 | 详情 |
| (XII) | 45754 | ethyl (2R,3R)-3-[4-bromo-2-(2-bromoethyl)butyl]-2,4-dimethyl-4-pentenoate | C15H26Br2O2 | 详情 | 详情 | |
| (XIII) | 45755 | ethyl (1R,2S,4R)-4-(2-bromoethyl)-2-isopropenyl-1-methylcyclohexanecarboxylate | 74181-34-3 | C15H25BrO2 | 详情 | 详情 |
| (XIV) | 45756 | ethyl (1R,2S,4R)-2-isopropenyl-1-methyl-4-vinylcyclohexanecarboxylate | C15H24O2 | 详情 | 详情 | |
| (XV) | 45757 | [(1R,2S,4R)-2-isopropenyl-1-methyl-4-vinylcyclohexyl]methanol | C13H22O | 详情 | 详情 | |
| (XVI) | 45758 | 1-[(1R,3S,4R)-4-(hydroxymethyl)-3-isopropenyl-4-methylcyclohexyl]-1-ethanone | C13H22O2 | 详情 | 详情 | |
| (XVII) | 45759 | (1R,2S,4R)-4-acetyl-2-isopropenyl-1-methylcyclohexanecarbaldehyde | C13H20O2 | 详情 | 详情 | |
| (XVIII) | 27301 | methylene(triphenyl)phosphorane | C19H17P | 详情 | 详情 |
合成路线10
该中间体在本合成路线中的序号：(X)4-Bromophenol (I) was acetylated with Ac2O and Et3N, and the resulting 4-bromophenyl acetate (II) was rearranged to 5'-bromo-2'-hydroxyacetophenone (III) in the presence of AlCl3 at 120 C. Subsequent nitration of (III) produced the 3'-nitroacetophenone (IV). The catalytic hydrogenation of the nitro group of (IV), with simultaneous halogen hydrogenolysis, furnished 3'-amino-2'-hydroxyacetophe-none (V). Then, diazotization of the amine group of (V), followed by treatment with KI and Cu powder gave iodide (VI). Coupling of 4-phenyl-1-butanol (VII) with 4-hydroxybenzaldehyde (VIII) under Mitsunobu conditions provided 4-(4-phenylbutoxy)benzaldehyde (IX). Further Wittig reaction of (IX) with methylene triphenylphosphorane (X) gave the styrene (XI). This was condensed with the iodoacetophenone (VI) in the presence of Pd(OAc)2 to produce the stilbene derivative (XII). The benzopyranone (XIII) was prepared by condensation of hydroxyacetophenone (XII) with diethyl oxalate in the presence of NaOEt, followed by acid cyclization. After conversion of the ester function of (XIII) to the corresponding amide with methanolic ammonia, dehydration using POCl3 in DMF afforded nitrile (XIV). The required tetrazole ring was finally obtained by reaction with NaN3 and NH4Cl in DMF at 100 C.
| 【1】 Carganico, G.; Mauleon Casellas, D.; Pascual Avellana, J.; Garcia Perez, M.L.; Palomer Benet, A. (Menarini Industrie Farma Riunite srl); Benzopyran derivs. having leukotriene-antagonistic action. EP 0888327; ES 2127106; JP 2000506878; US 5990142; WO 9734885 . |
| 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) | 25313 | 4-bromophenol | 106-41-2 | C6H5BrO | 详情 | 详情 |
| (II) | 27286 | 4-bromophenyl acetate | C8H7BrO2 | 详情 | 详情 | |
| (III) | 27287 | 1-(5-bromo-2-hydroxyphenyl)-1-ethanone | 1450-75-5 | C8H7BrO2 | 详情 | 详情 |
| (IV) | 27288 | 1-(5-bromo-2-hydroxy-3-nitrophenyl)-1-ethanone | C8H6BrNO4 | 详情 | 详情 | |
| (V) | 27289 | 1-(3-amino-2-hydroxyphenyl)-1-ethanone | C8H9NO2 | 详情 | 详情 | |
| (VI) | 27290 | 1-(2-hydroxy-3-iodophenyl)-1-ethanone | C8H7IO2 | 详情 | 详情 | |
| (VII) | 27291 | 4-phenyl-1-butanol | 3360-41-6 | C10H14O | 详情 | 详情 |
| (VIII) | 13433 | 4-Hydroxybenzaldehyde; p-Hydroxybenzaldehyde | 123-08-0 | C7H6O2 | 详情 | 详情 |
| (IX) | 27292 | 4-(4-phenylbutoxy)benzaldehyde | C17H18O2 | 详情 | 详情 | |
| (X) | 27301 | methylene(triphenyl)phosphorane | C19H17P | 详情 | 详情 | |
| (XI) | 27293 | 1-(4-phenylbutoxy)-4-vinylbenzene | C18H20O | 详情 | 详情 | |
| (XII) | 27294 | 1-(2-hydroxy-3-[(E)-2-[4-(4-phenylbutoxy)phenyl]ethenyl]phenyl)-1-ethanone | C26H26O3 | 详情 | 详情 | |
| (XIII) | 27295 | ethyl 4-oxo-8-[(E)-2-[4-(4-phenylbutoxy)phenyl]ethenyl]-4H-chromene-2-carboxylate | C30H28O5 | 详情 | 详情 | |
| (XIV) | 27296 | 4-oxo-8-[(E)-2-[4-(4-phenylbutoxy)phenyl]ethenyl]-4H-chromene-2-carbonitrile | C28H23NO3 | 详情 | 详情 |
合成路线11
该中间体在本合成路线中的序号：(XI)The reaction of the chiral epoxide (I) with 4-methoxybenzaldehyde (II) by means of NaAl(OMe)3H in THF gives the 1,3-dioxane (III), which is opened by reduction with DIBAL in dichloromethane to yield the chiral benzyl ether (IV). The oxidation of the primary alcohol of (IV) with DMP in dichloromethane affords the corresponding aldehyde (V), which is condensed with the boronate (VI) and S,S-diisopropyl tartrate in toluene to provide the unsaturated alcohol (VII).The protection of (VII) with Tbdps-Cl and imidazole yields the fully protected triol (VIII), which is oxidized at the terminal double bond with 9-BBN in THF to give the primary alcohol (IX). The oxidation of (IX) with DMP in dichloromethane affords the aldehyde (X), which is condensed with methylenetriphenylphosphorane (XI) in THF to provide the terminal olefin (XII). Elimination of the Pmb protecting group of (XII) with DDQ in dichloromethane gives the alcohol (XIII), which is esterified with 2-allyl-6-methoxybenzoic acid (XIV)(obtained by allylation of 2-methoxybenzoic acid (XV) with allyl bromide (XVI), BuLi and MgBr2) by means of DEAD and PPh3 yielding the ester (XVII). The cyclization of (XVII) by means of a metathesis reaction catalyzed by a ruthenium catalyst in refluxing dichloromethane affords the bicyclic lactone (XVIII), which is treated with BBr3 in dichloromethane to provide the dihydroxylated lactone (XIX).
| 【1】 Labrecque, D.; et al.; Enantioselective total synthesis of salicylihalamides A and B. Tetrahedron Lett 2001, 42, 14, 2645. |
| 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) | 47480 | [(2R,3R)-3-[3-(benzyloxy)propyl]oxiranyl]methanol | C13H18O3 | 详情 | 详情 | |
| (II) | 27251 | 4-methoxybenzaldehyde; Anisicaldehyde; p-anisaldehyde | 123-11-5 | C8H8O2 | 详情 | 详情 |
| (III) | 47481 | (4R)-4-[3-(benzyloxy)propyl]-2-(4-methoxyphenyl)-1,3-dioxane; benzyl 3-[(4R)-2-(4-methoxyphenyl)-1,3-dioxan-4-yl]propyl ether | C21H26O4 | 详情 | 详情 | |
| (IV) | 47482 | (3R)-6-(benzyloxy)-3-[(4-methoxybenzyl)oxy]-1-hexanol | C21H28O4 | 详情 | 详情 | |
| (V) | 47483 | (3R)-6-(benzyloxy)-3-[(4-methoxybenzyl)oxy]hexanal | C21H26O4 | 详情 | 详情 | |
| (VI) | 47484 | dimethyl (E)-2-butenylboronate | C6H13BO2 | 详情 | 详情 | |
| (VII) | 47485 | (3S,4R,6R)-9-(benzyloxy)-6-[(4-methoxybenzyl)oxy]-3-methyl-1-nonen-4-ol | C25H34O4 | 详情 | 详情 | |
| (VIII) | 47486 | [((1R,2S)-1-[(2R)-5-(benzyloxy)-2-[(4-methoxybenzyl)oxy]pentyl]-2-methyl-3-butenyl)oxy](tert-butyl)diphenylsilane; benzyl (4R,6R,7S)-6-[[tert-butyl(diphenyl)silyl]oxy]-4-[(4-methoxybenzyl)oxy]-7-methyl-8-nonenyl ether | C41H52O4Si | 详情 | 详情 | |
| (IX) | 47487 | (3S,4R,6R)-9-(benzyloxy)-4-[[tert-butyl(diphenyl)silyl]oxy]-6-[(4-methoxybenzyl)oxy]-3-methyl-1-nonanol | C41H54O5Si | 详情 | 详情 | |
| (X) | 47488 | (3S,4R,6R)-9-(benzyloxy)-4-[[tert-butyl(diphenyl)silyl]oxy]-6-[(4-methoxybenzyl)oxy]-3-methylnonanal | C41H52O5Si | 详情 | 详情 | |
| (XI) | 27301 | methylene(triphenyl)phosphorane | C19H17P | 详情 | 详情 | |
| (XII) | 47489 | [((1R,2S)-1-[(2R)-5-(benzyloxy)-2-[(4-methoxybenzyl)oxy]pentyl]-2-methyl-4-pentenyl)oxy](tert-butyl)diphenylsilane; benzyl (4R,6R,7S)-6-[[tert-butyl(diphenyl)silyl]oxy]-4-[(4-methoxybenzyl)oxy]-7-methyl-9-decenyl ether | C42H54O4Si | 详情 | 详情 | |
| (XIII) | 47490 | (4R,6R,7S)-1-(benzyloxy)-6-[[tert-butyl(diphenyl)silyl]oxy]-7-methyl-9-decen-4-ol | C34H46O3Si | 详情 | 详情 | |
| (XIV) | 13926 | 2-Methoxybenzoic acid; o-Methoxybenzoic Acid | 579-75-9 | C8H8O3 | 详情 | 详情 |
| (XV) | 11463 | 3-Bromo-1-propene; 3-Bromopropene；allyl bromide | 106-95-6 | C3H5Br | 详情 | 详情 |
| (XVI) | 47491 | 2-allyl-6-methoxybenzoic acid | C11H12O3 | 详情 | 详情 | |
| (XVII) | 47492 | (1S,3R,4S)-1-[3-(benzyloxy)propyl]-3-[[tert-butyl(diphenyl)silyl]oxy]-4-methyl-6-heptenyl 2-allyl-6-methoxybenzoate | C45H56O5Si | 详情 | 详情 | |
| (XVIII) | 47493 | (3S,5R,6S)-3-[3-(benzyloxy)propyl]-5-[[tert-butyl(diphenyl)silyl]oxy]-14-methoxy-6-methyl-3,4,5,6,7,10-hexahydro-1H-2-benzoxacyclododecin-1-one | C43H52O5Si | 详情 | 详情 | |
| (XIX) | 47494 | (3S,5R,6S)-5-[[tert-butyl(diphenyl)silyl]oxy]-14-hydroxy-3-(3-hydroxypropyl)-6-methyl-3,4,5,6,7,10-hexahydro-1H-2-benzoxacyclododecin-1-one | C35H44O5Si | 详情 | 详情 |
合成路线12
该中间体在本合成路线中的序号：(XI)The reaction of the chiral epoxide (I) with 4-methoxybenzaldehyde (II) by means of NaAl(OMe)3H in THF gives the 1,3-dioxane (III), which is opened by reduction with DIBAL in dichloromethane to yield the chiral benzyl ether (IV). The oxidation of the primary alcohol of (IV) with DMP in dichloromethane affords the corresponding aldehyde (V), which is condensed with the boronate (VI) and S,S-diisopropyl tartrate in toluene to provide the unsaturated alcohol (VII).The protection of (VII) with Tbdps-Cl and imidazole yields the fully protected triol (VIII), which is oxidized at the terminal double bond with 9-BBN in THF to give the primary alcohol (IX). The oxidation of (IX) with DMP in dichloromethane affords the aldehyde (X), which is condensed with methylenetriphenylphosphorane (XI) in THF to provide the terminal olefin (XII). Elimination of the Pmb protecting group of (XII) with DDQ in dichloromethane gives the alcohol (XIII), which is esterified with 2-allyl-6-methoxybenzoic acid (XIV)(obtained by allylation of 2-methoxybenzoic acid (XV) with allyl bromide (XVI), BuLi and MgBr2) by means of DEAD and PPh3 yielding the ester (XVII). The cyclization of (XVII) by means of a metathesis reaction catalyzed by a ruthenium catalyst in refluxing dichloromethane affords the bicyclic lactone (XVIII), which is treated with BBr3 in dichloromethane to provide the dihydroxylated lactone (XIX).
| 【1】 Labrecque, D.; et al.; Enantioselective total synthesis of salicylihalamides A and B. Tetrahedron Lett 2001, 42, 14, 2645. |
| 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) | 47480 | [(2R,3R)-3-[3-(benzyloxy)propyl]oxiranyl]methanol | C13H18O3 | 详情 | 详情 | |
| (II) | 27251 | 4-methoxybenzaldehyde; Anisicaldehyde; p-anisaldehyde | 123-11-5 | C8H8O2 | 详情 | 详情 |
| (III) | 47481 | (4R)-4-[3-(benzyloxy)propyl]-2-(4-methoxyphenyl)-1,3-dioxane; benzyl 3-[(4R)-2-(4-methoxyphenyl)-1,3-dioxan-4-yl]propyl ether | C21H26O4 | 详情 | 详情 | |
| (IV) | 47482 | (3R)-6-(benzyloxy)-3-[(4-methoxybenzyl)oxy]-1-hexanol | C21H28O4 | 详情 | 详情 | |
| (V) | 47483 | (3R)-6-(benzyloxy)-3-[(4-methoxybenzyl)oxy]hexanal | C21H26O4 | 详情 | 详情 | |
| (VI) | 47484 | dimethyl (E)-2-butenylboronate | C6H13BO2 | 详情 | 详情 | |
| (VII) | 47485 | (3S,4R,6R)-9-(benzyloxy)-6-[(4-methoxybenzyl)oxy]-3-methyl-1-nonen-4-ol | C25H34O4 | 详情 | 详情 | |
| (VIII) | 47486 | [((1R,2S)-1-[(2R)-5-(benzyloxy)-2-[(4-methoxybenzyl)oxy]pentyl]-2-methyl-3-butenyl)oxy](tert-butyl)diphenylsilane; benzyl (4R,6R,7S)-6-[[tert-butyl(diphenyl)silyl]oxy]-4-[(4-methoxybenzyl)oxy]-7-methyl-8-nonenyl ether | C41H52O4Si | 详情 | 详情 | |
| (IX) | 47487 | (3S,4R,6R)-9-(benzyloxy)-4-[[tert-butyl(diphenyl)silyl]oxy]-6-[(4-methoxybenzyl)oxy]-3-methyl-1-nonanol | C41H54O5Si | 详情 | 详情 | |
| (X) | 47488 | (3S,4R,6R)-9-(benzyloxy)-4-[[tert-butyl(diphenyl)silyl]oxy]-6-[(4-methoxybenzyl)oxy]-3-methylnonanal | C41H52O5Si | 详情 | 详情 | |
| (XI) | 27301 | methylene(triphenyl)phosphorane | C19H17P | 详情 | 详情 | |
| (XII) | 47489 | [((1R,2S)-1-[(2R)-5-(benzyloxy)-2-[(4-methoxybenzyl)oxy]pentyl]-2-methyl-4-pentenyl)oxy](tert-butyl)diphenylsilane; benzyl (4R,6R,7S)-6-[[tert-butyl(diphenyl)silyl]oxy]-4-[(4-methoxybenzyl)oxy]-7-methyl-9-decenyl ether | C42H54O4Si | 详情 | 详情 | |
| (XIII) | 47490 | (4R,6R,7S)-1-(benzyloxy)-6-[[tert-butyl(diphenyl)silyl]oxy]-7-methyl-9-decen-4-ol | C34H46O3Si | 详情 | 详情 | |
| (XIV) | 13926 | 2-Methoxybenzoic acid; o-Methoxybenzoic Acid | 579-75-9 | C8H8O3 | 详情 | 详情 |
| (XV) | 11463 | 3-Bromo-1-propene; 3-Bromopropene；allyl bromide | 106-95-6 | C3H5Br | 详情 | 详情 |
| (XVI) | 47491 | 2-allyl-6-methoxybenzoic acid | C11H12O3 | 详情 | 详情 | |
| (XVII) | 47492 | (1S,3R,4S)-1-[3-(benzyloxy)propyl]-3-[[tert-butyl(diphenyl)silyl]oxy]-4-methyl-6-heptenyl 2-allyl-6-methoxybenzoate | C45H56O5Si | 详情 | 详情 | |
| (XVIII) | 47493 | (3S,5R,6S)-3-[3-(benzyloxy)propyl]-5-[[tert-butyl(diphenyl)silyl]oxy]-14-methoxy-6-methyl-3,4,5,6,7,10-hexahydro-1H-2-benzoxacyclododecin-1-one | C43H52O5Si | 详情 | 详情 | |
| (XIX) | 47494 | (3S,5R,6S)-5-[[tert-butyl(diphenyl)silyl]oxy]-14-hydroxy-3-(3-hydroxypropyl)-6-methyl-3,4,5,6,7,10-hexahydro-1H-2-benzoxacyclododecin-1-one | C35H44O5Si | 详情 | 详情 |