5-allyloxy-3-bromo-7-(tert-butyldiphenylsilyloxy)-1,4-bis(methoxymethoxy)-2,6-dimethylnaphthalene | 198124-46-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 5-allyloxy-3-bromo-7-(tert-butyldiphenylsilyloxy)-1,4-bis(methoxymethoxy)-2,6-dimethylnaphthalene
• 英文别名: [6-Bromo-5,8-bis(methoxymethoxy)-3,7-dimethyl-4-prop-2-enoxynaphthalen-2-yl]oxy-tert-butyl-diphenylsilane
• CAS: 198124-46-8
• 化学式: C₃₅H₄₁BrO₆Si
• 分子量: 665.696
• InChiKey: CYJBKPMCDGVDEP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.69
• 重原子数：
  43
• 可旋转键数：
  14
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  5-allyloxy-3-bromo-7-(tert-butyldiphenylsilyloxy)-1,4-bis(methoxymethoxy)-2,6-dimethylnaphthalene 在 盐酸 、 lithium hydroxide 、 N-溴代丁二酰亚胺(NBS) 、 四(三苯基膦)钯 、 正丁基锂 、 草酰氯 、 18-冠醚-6 、 二苯基膦叠氮化物 、 氢氟酸 、 四丁基氟化铵 、 2-氯-1-甲基吡啶碘化物 、 三正丁基氢锡 、 双(三甲基硅烷基)氨基钾 、 二异丁基氢化铝 、 戴斯-马丁氧化剂 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 triethylamine tris(hydrogen fluoride) 、 三乙胺 、 N,N-二异丙基乙胺 、 三苯基膦 、 tris(dimethylamino)sulfonium trimethylsilyldifluoride 、 lithium chloride 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 氯仿 、 水 、 溶剂黄146 、 二甲基亚砜 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 生成 (7E,18Z,20E)-(9S,10S,11R,12R,13R,14R,15R,16R,17R)-2,4,10,12,14,16-Hexahydroxy-26,28-bis-methoxymethoxy-3,7,9,11,15,17,21,25-octamethyl-6,22-dioxo-23-aza-tricyclo[22.3.1.0^5,27]octacosa-1(27),2,4,7,18,20,24(28),25-octaene-13-carboxylic acid
  参考文献：
  名称：

  Total Synthesis of (+)-Damavaricin D

  摘要：

  DOI：

  10.1021/ja971828x
• 作为产物：
  描述：

  5-Allyloxy-3-bromo-7-hydroxy-2,6-dimethyl-[1,4]naphthoquinone 在 咪唑 、 sodium dithionite 、 Adogen 464(R) 作用下， 以 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 19.5h， 生成 5-allyloxy-3-bromo-7-(tert-butyldiphenylsilyloxy)-1,4-bis(methoxymethoxy)-2,6-dimethylnaphthalene
  参考文献：
  名称：

  Synthesis of highly functionalized naphthoate precursors to damavaricin D — Observation of kinetically stable benzocyclohexadienones in the bromination reactions of highly functionalized β-naphthol derivatives

  摘要：

  Selective syntheses of the highly substituted bromonaphthoates 4a, 4b, 19, and 22 are reported. These compounds were targeted as precursors to the naphthoquinone nucleus of damavaricin D; compound 22 ultimately was used in the successful total synthesis. The synthesis of 22 features the Diels-Alder reaction of the oxygenated diene 5 and 2,6-dibromo-3-methylbenzoquinone 6 to establish the core naphthalenic unit. The quinone was protected throughout this synthesis as a 1,4-bis-methoxymethyl-1,4-dihydroquinone (see 36). The C-2-carboalkoxy group of 22 was added by carboxylation of the aryllithium intermediate generated from 36, and protected as a beta -trimethylsilylethyl ester. Finally, the C-8-Br substituent was introduced by NBS bromination of 38. This reaction proceeds by way of bromobenzocyclohexadienone 39. Related bromobenzo-cyclohexadienones 13 and 29 were observed in the NBS brominations of the highly functionalized beta -naphthyl MOM ethers 11 and 28. The bromobenzocyclohexadienones 29 and 39 undergo facile substitution reactions with chloride ion and reduction with bromide ion at rates competitive with base-promoted aromatization. The surprising kinetic stability of these intermediates is attributed to a combination of steric and stereoelectronic factors.

  DOI：

  10.1139/cjc-79-11-1711

文献信息

• Synthesis of highly functionalized naphthoate precursors to damavaricin D — Observation of kinetically stable benzocyclohexadienones in the bromination reactions of highly functionalized β-naphthol derivatives
  作者：William R. Roush、David J. Madar、D. Scott Coffey

  DOI：10.1139/cjc-79-11-1711

  日期：——

  Selective syntheses of the highly substituted bromonaphthoates 4a, 4b, 19, and 22 are reported. These compounds were targeted as precursors to the naphthoquinone nucleus of damavaricin D; compound 22 ultimately was used in the successful total synthesis. The synthesis of 22 features the Diels-Alder reaction of the oxygenated diene 5 and 2,6-dibromo-3-methylbenzoquinone 6 to establish the core naphthalenic unit. The quinone was protected throughout this synthesis as a 1,4-bis-methoxymethyl-1,4-dihydroquinone (see 36). The C-2-carboalkoxy group of 22 was added by carboxylation of the aryllithium intermediate generated from 36, and protected as a beta -trimethylsilylethyl ester. Finally, the C-8-Br substituent was introduced by NBS bromination of 38. This reaction proceeds by way of bromobenzocyclohexadienone 39. Related bromobenzo-cyclohexadienones 13 and 29 were observed in the NBS brominations of the highly functionalized beta -naphthyl MOM ethers 11 and 28. The bromobenzocyclohexadienones 29 and 39 undergo facile substitution reactions with chloride ion and reduction with bromide ion at rates competitive with base-promoted aromatization. The surprising kinetic stability of these intermediates is attributed to a combination of steric and stereoelectronic factors.
• Total Synthesis of (+)-Damavaricin D
  作者：William R. Roush、D. Scott Coffey、David J. Madar

  DOI：10.1021/ja971828x

  日期：1997.11.1