【结 构 式】 |
【分子编号】27119 【品名】3-[[tert-butyl(dimethyl)silyl]oxy]-2-[1-(1-hydroxy-1-methyl-2-propynyl)cyclopropyl]-5-(trimethylsilyl)-4-pentyn-2-ol 【CA登记号】 |
【 分 子 式 】C21H38O3Si2 【 分 子 量 】394.70192 【元素组成】C 63.9% H 9.7% O 12.16% Si 14.23% |
合成路线1
该中间体在本合成路线中的序号:(V)Racemic compound.- The reaction of 1,1-diacetylcyclopropane (I) with the disilylated propargyl alcohol (II) by means of tert-butyllithium gives the monocondensation compound (III), which is treated with ethynylmagnesium bromide (IV) and CeCl3 to yield the bis acetylenic diol (V). The acylation of (V) with acetic anhydridde affords the monoacetate (VI), which is isomerized by means of [CuH(PPh3]6 to provide the allene compound (VII). The selective deprotection of (VII) gives the terminal acetylene (VIII), which is cyclized with Mo(CO)6 in refluxing DMSO/toleuene to afford the tricyclic ketone (IX). The methyletion of (IX) with CH3Li gives the monosilylated tricyclic diol (X), which is deprotected with TBAF yielding the diol (XI). The oxidation of the secondary alcohol of (XI) with Dess Martin periodinane (DMP) provides the tricyclic ketone (XII), which is finally hydroxymethylated with formaldehyde and sulfuric acid to afford the target compound as a racemic mixture.
【1】 Brummond, K.M.; Lu, J.; A short synthesis of the potent antitumor agent (±)-hydroxymethylacylfulvene using allenic pauson-khand type cycloaddition. J Am Chem Soc 1999, 121, 21, 5087. |
【2】 Brummond, K.M.; et al.; A rapid synthesis of hydroxymethylacylfulvene (HMAF) using the allenic Pauson - Khand reaction. A synthetic approach to either enantiomer of this illudane structure. J Am Chem Soc 2000, 122, 20, 4915. |
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) | 27116 | 1-(1-acetylcyclopropyl)-1-ethanone | C7H10O2 | 详情 | 详情 | |
(II) | 27117 | tert-butyl(dimethyl)silyl 3-(trimethylsilyl)-2-propynyl ether | C12H26OSi2 | 详情 | 详情 | |
(III) | 27118 | 1-[1-[2-[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-1-methyl-4-(trimethylsilyl)-3-butynyl]cyclopropyl]-1-ethanone | C19H36O3Si2 | 详情 | 详情 | |
(IV) | 17778 | ETHYNYLMAGNESIUM BROMIDE; bromo(ethynyl)magnesium | 4301-14-8 | C2HBrMg | 详情 | 详情 |
(V) | 27119 | 3-[[tert-butyl(dimethyl)silyl]oxy]-2-[1-(1-hydroxy-1-methyl-2-propynyl)cyclopropyl]-5-(trimethylsilyl)-4-pentyn-2-ol | C21H38O3Si2 | 详情 | 详情 | |
(VI) | 27120 | 1-[1-[2-[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-1-methyl-4-(trimethylsilyl)-3-butynyl]cyclopropyl]-1-methyl-2-propynyl acetate | C23H40O4Si2 | 详情 | 详情 | |
(VII) | 27121 | 3-[[tert-butyl(dimethyl)silyl]oxy]-2-[1-(1-methyl-1,2-propadienyl)cyclopropyl]-5-(trimethylsilyl)-4-pentyn-2-ol | C21H38O2Si2 | 详情 | 详情 | |
(VIII) | 27122 | 3-[[tert-butyl(dimethyl)silyl]oxy]-2-[1-(1-methyl-1,2-propadienyl)cyclopropyl]-4-pentyn-2-ol | C18H30O2Si | 详情 | 详情 | |
(IX) | 27123 | 4'-(Tert-butyldimethylsilyloxy)-5'-hydroxy-5',7'-dimethyl-2',4',5',6'-tetrahydro-1'H-spiro[cyclopropane-1,6'-inden]-2'-one | C19H30O3Si | 详情 | 详情 | |
(X) | 27124 | 7'-(Tert-butyldimethylsilyloxy)-2',4',6'-trimethyl-6',7'-dihydro-5'H-spiro[cyclopropane-1,5'-inden]-6'-ol | C20H32O2Si | 详情 | 详情 | |
(XI) | 27125 | 2',4',6'-Trimethyl-6',7'-dihydro-5'H-spiro[cyclopropane-1,5'-indene]-6',7'-diol | C14H18O2 | 详情 | 详情 | |
(XII) | 27126 | 6'-Hydroxy-2',4',6'-trimethyl-6',7'-dihydro-5'H-spiro[cyclopropane-1,5'-inden]-7'-one | C14H16O2 | 详情 | 详情 |