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【结 构 式】 
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【分子编号】62944 【品名】[(1E,3S)-3-(allyloxy)-5-methyl-1,5-hexadienyl](methyl)zinc 【CA登记号】 |
【 分 子 式 】C11H18OZn 【 分 子 量 】231.65332 【元素组成】C 57.03% H 7.83% O 6.91% Zn 28.23% |
合成路线1
该中间体在本合成路线中的序号：(XI)Synthesis of the aldehydic epoxide intermediate (XIV): The reaction of the protected diol (IX) with propanedithiol and BF3/Et2O, followed by reation with p-MeO-C6H4CH(OMe)2 and TsOH, reductive cleavage with DIBAL, and final oxidation with TPAP gives the chiral aldeyde (X). The condensation of (X) with the organozinc derivative (XI) in dichloromethane gives the secondary alcohol (XII), which is silylated by means of TBDMS-OTf and DIEA and submitted to a ring closing metathesis reaction catalyzed by a Ru catalyst yielding the dihydropyran derivative (XIII). Finally this compound is desilylated and epoxidized by means of PPTS ant tBu-OOH in the presence of (+)-DET, and oxidized with DMP to afford the target the aldehydic epoxide intermediate (XIV).
| 【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 |
|---|---|---|---|---|---|---|
| (IX) | 62942 | tert-butyl(dimethyl)silyl (E)-4-[(4S)-2,2-diethyl-1,3-dioxolan-4-yl]-2-butenyl ether; tert-butyl({(E)-4-[(4S)-2,2-diethyl-1,3-dioxolan-4-yl]-2-butenyl}oxy)dimethylsilane | C17H34O3Si | 详情 | 详情 | |
| (X) | 62943 | (2S,4E)-2-(2-[1,1'-biphenyl]-4-ylethoxy)-6-{[tert-butyl(dimethyl)silyl]oxy}-4-hexenal | C26H36O3Si | 详情 | 详情 | |
| (XI) | 62944 | [(1E,3S)-3-(allyloxy)-5-methyl-1,5-hexadienyl](methyl)zinc | C11H18OZn | 详情 | 详情 | |
| (XII) | 62945 | (2E,5S,6S,7E,9S)-9-(allyloxy)-5-(2-[1,1'-biphenyl]-4-ylethoxy)-1-{[tert-butyl(dimethyl)silyl]oxy}-11-methyl-2,7,11-dodecatrien-6-ol | C36H52O4Si | 详情 | 详情 | |
| (XIII) | 62946 | (1S,2S,4E)-2-(2-[1,1'-biphenyl]-4-ylethoxy)-6-{[tert-butyl(dimethyl)silyl]oxy}-1-{(E)-2-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]ethenyl}-4-hexenyl tert-butyl(dimethyl)silyl ether; 4-{2-[((1S,3E)-5-{[tert-butyl(dimethyl)silyl]oxy}-1-{(1S,2E)-1-{[tert-butyl(dimethyl)silyl]oxy}-3-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]-2-propenyl}-3-pentenyl)oxy]ethyl}-1,1'-biphenyl | C40H62O4Si2 | 详情 | 详情 | |
| (XIV) | 62947 | (2S)-3-{(2S,3S,4E)-2-(2-[1,1'-biphenyl]-4-ylethoxy)-3-{[tert-butyl(dimethyl)silyl]oxy}-5-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]-4-pentenyl}-2-oxiranecarbaldehyde | C34H46O5Si | 详情 | 详情 |