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【结 构 式】 
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【分子编号】28785 【品名】3,6-Bis[2-(trimethylsilyl)ethylsulfanyl]octa-3,5-dien-1,7-diyne dilithium salt 【CA登记号】 |
【 分 子 式 】C18H28Li2S2Si2 【 分 子 量 】378.60532 【元素组成】C 57.1% H 7.45% Li 3.67% S 16.94% Si 14.84% |
合成路线1
该中间体在本合成路线中的序号：(VI)The addition of 2-(trimethylsilyl)ethylmercaptane (I) to 2,4-hexadiyn-1,6-diol (II) catalyzed by KOH in DMF gives the addition product (III), which is oxidized with Dess-Martin periodinane in dichloromethane or oxalyl chloride in DMSO yielding the dialdehyde (IV). The condensation of (IV) with tetrabromomethane by means of triphenylphosphine in dichloromethane affords the tetrabromo derivative (V), which is treated with butyllithium in THF to give the diacetylenic dianion (VI). The reaction of (V) with methyl iodide yields the methylated monoanion (VII), which is condensed with DMF catalyzed by boron trifluoride ethearate to afford the diacetylenic aldehyde (VIII). The reaction of (VIII) with tetrabromomethane/triphenylphosphine as before gives the dibromovinyl derivative (IX), which is treated with butyllithium as before yielding the triacetylenic compound (X). The condensation of (X) with vinyl bromide (XI) by means of Pd(PPh3)4/CuI/triethylamine in toluene affords the intermediate (XII), which is finally submitted to an oxidative cyclization by means of tetrabutylammonium fluoride and iodine.
| 【1】 Yang, W.; Koreeda, M.; Chemistry of 1,2-dithiins. Synthesis of the potent antibiotic thiarubrine A. J Am Chem Soc 1994, 116, 10793. |
| 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) | 28780 | 2,4-hexadiyne-1,6-diol | 3031-68-3 | C6H6O2 | 详情 | 详情 |
| (II) | 28781 | 2-(trimethylsilyl)-1-ethanethiol | 18143-30-1 | C5H14SSi | 详情 | 详情 |
| (III) | 28782 | (2Z,4Z)-2,5-bis[[2-(trimethylsilyl)ethyl]sulfanyl]-2,4-hexadiene-1,6-diol | C16H34O2S2Si2 | 详情 | 详情 | |
| (IV) | 28783 | (2Z,4Z)-2,5-bis[[2-(trimethylsilyl)ethyl]sulfanyl]-2,4-hexadienedial | C16H30O2S2Si2 | 详情 | 详情 | |
| (V) | 28784 | (1Z,3Z)-6,6-dibromo-1-(2,2-dibromovinyl)-4-[[2-(trimethylsilyl)ethyl]sulfanyl]-1,3,5-hexatrienyl 2-(trimethylsilyl)ethyl sulfide | C18H30Br4S2Si2 | 详情 | 详情 | |
| (VI) | 28785 | 3,6-Bis[2-(trimethylsilyl)ethylsulfanyl]octa-3,5-dien-1,7-diyne dilithium salt | C18H28Li2S2Si2 | 详情 | 详情 | |
| (VII) | 28786 | ((3Z,5Z)-3,6-bis[[2-(trimethylsilyl)ethyl]sulfanyl]-3,5-nonadiene-1,7-diynyl)lithium | C19H31LiS2Si2 | 详情 | 详情 | |
| (VIII) | 28787 | (4Z,6Z)-4,7-bis[[2-(trimethylsilyl)ethyl]sulfanyl]-4,6-decadiene-2,8-diynal | C20H32OS2Si2 | 详情 | 详情 | |
| (IX) | 28788 | (1Z,3Z)-1-(4,4-dibromo-3-buten-1-ynyl)-4-[[2-(trimethylsilyl)ethyl]sulfanyl]-1,3-heptadien-5-ynyl 2-(trimethylsilyl)ethyl sulfide | C21H32Br2S2Si2 | 详情 | 详情 | |
| (X) | 28789 | (1Z,3Z)-1-(1,3-butadiynyl)-4-[[2-(trimethylsilyl)ethyl]sulfanyl]-1,3-heptadien-5-ynyl 2-(trimethylsilyl)ethyl sulfide | C21H32S2Si2 | 详情 | 详情 | |
| (XI) | 28790 | 1-bromoethylene | 593-60-2 | C2H3Br | 详情 | 详情 |
| (XII) | 28791 | (1Z,3Z)-1-(5-hexene-1,3-diynyl)-4-[[2-(trimethylsilyl)ethyl]sulfanyl]-1,3-heptadien-5-ynyl 2-(trimethylsilyl)ethyl sulfide | C23H34S2Si2 | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(VI)The addition of 2-(trimethylsilyl)ethylmercaptane (I) to 2,4-hexadiyn-1,6-diol (II) catalyzed by KOH in DMF gives the addition product (III), which is oxidized with Dess-Martin periodinane in dichloromethane or oxalyl chloride in DMSO yielding the dialdehyde (IV). The condensation of (IV) with tetrabromomethane by means of triphenylphosphine in dichloromethane affords the tetrabromo derivative (V), which is treated with butyllithium in THF to give the diacetylenic dianion (VI). The reaction of (V) with methyl iodide yields the mono methylated compound (VII), which is condensed with cis-1,2-dichloroethylene (VIII) by means of Pd(PPh3)4/CuI/butylamine in benzene affording the cis-chlorovinyl compound (IX). THe reaction of (IX) with vinylmagnesium bromide (X) catalyzed by Pd(PPh3)4 in benzene gives precursor (XI), which is finally submitted to an oxidative cyclization by means of tetrabutylammonium fluoride/trifluoroacetic acid and iodine.
| 【1】 Wang, Y.M.; et al.; Total synthesis and DNA-cleaving properties of thiarubrine C. J Org Chem 1998, 63, 24, 8644. |
| 【2】 Yang, W.; Koreeda, M.; Chemistry of 1,2-dithiins. Synthesis of the potent antibiotic thiarubrine A. J Am Chem Soc 1994, 116, 10793. |
| 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) | 28780 | 2,4-hexadiyne-1,6-diol | 3031-68-3 | C6H6O2 | 详情 | 详情 |
| (II) | 28781 | 2-(trimethylsilyl)-1-ethanethiol | 18143-30-1 | C5H14SSi | 详情 | 详情 |
| (III) | 28782 | (2Z,4Z)-2,5-bis[[2-(trimethylsilyl)ethyl]sulfanyl]-2,4-hexadiene-1,6-diol | C16H34O2S2Si2 | 详情 | 详情 | |
| (IV) | 28783 | (2Z,4Z)-2,5-bis[[2-(trimethylsilyl)ethyl]sulfanyl]-2,4-hexadienedial | C16H30O2S2Si2 | 详情 | 详情 | |
| (V) | 28784 | (1Z,3Z)-6,6-dibromo-1-(2,2-dibromovinyl)-4-[[2-(trimethylsilyl)ethyl]sulfanyl]-1,3,5-hexatrienyl 2-(trimethylsilyl)ethyl sulfide | C18H30Br4S2Si2 | 详情 | 详情 | |
| (VI) | 28785 | 3,6-Bis[2-(trimethylsilyl)ethylsulfanyl]octa-3,5-dien-1,7-diyne dilithium salt | C18H28Li2S2Si2 | 详情 | 详情 | |
| (VII) | 28786 | ((3Z,5Z)-3,6-bis[[2-(trimethylsilyl)ethyl]sulfanyl]-3,5-nonadiene-1,7-diynyl)lithium | C19H31LiS2Si2 | 详情 | 详情 | |
| (VIII) | 28793 | (Z)-1,2-dichloroethene | 156-59-2 | C2H2Cl2 | 详情 | 详情 |
| (IX) | 28792 | (1Z,3Z)-1-[(Z)-4-chloro-3-buten-1-ynyl]-4-[[2-(trimethylsilyl)ethyl]sulfanyl]-1,3-heptadien-5-ynyl 2-(trimethylsilyl)ethyl sulfide | C21H33ClS2Si2 | 详情 | 详情 | |
| (X) | 16524 | bromo(vinyl)magnesium | 1826-67-1 | C2H3BrMg | 详情 | 详情 |
| (XI) | 28794 | (1Z,3Z)-1-[(3Z)-3,5-hexadien-1-ynyl]-4-[[2-(trimethylsilyl)ethyl]sulfanyl]-1,3-heptadien-5-ynyl 2-(trimethylsilyl)ethyl sulfide | C23H36S2Si2 | 详情 | 详情 |