8-allyloxy-6-(tert-butyldiphenylsilyloxy)-1,4-bis(methoxymethoxy)-3,7-dimethylnaphthalene-2-carboxylic acid β-trimethylsilylethyl ester | 198124-47-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 8-allyloxy-6-(tert-butyldiphenylsilyloxy)-1,4-bis(methoxymethoxy)-3,7-dimethylnaphthalene-2-carboxylic acid β-trimethylsilylethyl ester
• 英文别名: 2-Trimethylsilylethyl 6-[tert-butyl(diphenyl)silyl]oxy-1,4-bis(methoxymethoxy)-3,7-dimethyl-8-prop-2-enoxynaphthalene-2-carboxylate
• CAS: 198124-47-9
• 化学式: C₄₁H₅₄O₈Si₂
• 分子量: 731.046
• InChiKey: ACCGAQABQJCXQR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.42
• 重原子数：
  51
• 可旋转键数：
  19
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  81.7
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  8-allyloxy-6-(tert-butyldiphenylsilyloxy)-1,4-bis(methoxymethoxy)-3,7-dimethylnaphthalene-2-carboxylic acid β-trimethylsilylethyl ester 在 N-溴代丁二酰亚胺(NBS) 、 正丁基锂 、 草酰氯 、 18-冠醚-6 、 氢氟酸 、 双(三甲基硅烷基)氨基钾 、 戴斯-马丁氧化剂 、 triethylamine tris(hydrogen fluoride) 、 三乙胺 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 氯仿 、 二甲基亚砜 、 乙腈 为溶剂， 生成 2-trimethylsilylethyl 5-[(E,4S,5S,6R,7R,8R)-5,7-diacetyloxy-8-[(4R,5R,6R)-6-[(Z,2R)-5-methoxy-5-oxopent-3-en-2-yl]-2,2,5-trimethyl-1,3-dioxan-4-yl]-2,4,6-trimethyl-9-oxo-9-prop-2-enoxynon-2-enoyl]-1,4,6-tris(methoxymethoxy)-3,7-dimethyl-8-prop-2-enoxynaphthalene-2-carboxylate
  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-(tert-butyldiphenylsilyloxy)-1,4-bis(methoxymethoxy)-2,6-dimethylnaphthalene 在 正丁基锂 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 为溶剂， 反应 1.33h， 生成 8-allyloxy-6-(tert-butyldiphenylsilyloxy)-1,4-bis(methoxymethoxy)-3,7-dimethylnaphthalene-2-carboxylic acid β-trimethylsilylethyl ester
  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