(4'α,4'aα,8'α,8'aα)-4'-<(tert-Butyldimethylsilyl)oxy>octahydro-4'a,8'-dimethylspiro<1,3-dioxolane-2,7'(6'H)-naphthalen>-1'(2'H)-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4'α,4'aα,8'α,8'aα)-4'-<(tert-Butyldimethylsilyl)oxy>octahydro-4'a,8'-dimethylspiro<1,3-dioxolane-2,7'(6'H)-naphthalen>-1'(2'H)-one
• 英文别名: (4'S,4'aS,8'R,8'aR)-4'-[tert-butyl(dimethyl)silyl]oxy-4'a,8'-dimethylspiro[1,3-dioxolane-2,7'-3,4,5,6,8,8a-hexahydro-2H-naphthalene]-1'-one
• 化学式: C₂₀H₃₆O₄Si
• 分子量: 368.589
• InChiKey: PVASQLVYSOKZHO-QSOKESPWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.54
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2-乙基-2-甲基-1,3-二氧杂烷 、 (4S,4aS)-4-[tert-butyl(dimethyl)silyl]oxy-4a,8-dimethyl-3,4,5,6,8,8a-hexahydro-2H-naphthalene-1,7-dione 在 camphor-10-sulfonic acid 、 sodium methylate 、 乙二醇 作用下， 生成 (4'α,4'aα,8'α,8'aα)-4'-<(tert-Butyldimethylsilyl)oxy>octahydro-4'a,8'-dimethylspiro<1,3-dioxolane-2,7'(6'H)-naphthalen>-1'(2'H)-one 、 (4'α,4'aα,8'β,8'aβ)-4'-<(tert-Butyldimethylsilyl)oxy>octahydro-4'a,8'-dimethylspiro<1,3-dioxolane-2,7'(6'H)-naphthalen>-1'(2'H)-one
  参考文献：
  名称：

  Substituent Effects on Through-Bond Orbital Interaction-Induced Heterolysis of Some Perhydronaphthalenediol Monosulfonate Esters

  摘要：

  Substituent effects on the heterolysis of the perhydronaphthalene-1,4-diol monosulfonate esters 1, 7, and 8 induced by through-bond interactions (TBI) were studied. Evidence is found that, next to TBI, sigma-participation is the most important stereoelectronic effect which determines the reactivity of these compounds under strongly basic conditions in refluxing benzene. Substituents at carbon atoms adjacent to the carbon atom bearing the sulfonate ester group increase the contribution of a-participation which is expressed in a higher reactivity of these compounds. The product composition is primarily dependent on the degree of substitution at C(4). Homofragmentation and elimination are found when C(4) is unsubstituted as the reaction of mesylate 1 shows. Due to the repulsive 1,3-peri effect between the equatorial Me groups at C(4) and C(6) in the reaction of 7 and a combination of this 1,3-peri effect and the 4,4-dimethyl effect in that of 8, the ideal W arrangement is distorted. Consequently, no homofragmentation is observed with these compounds, and other reaction pathways (elimination, 1,3-H and 1,2-Me shifts) are now favored.

  DOI：

  10.1021/jo00118a045

文献信息

• Substituent Effects on Through-Bond Orbital Interaction-Induced Heterolysis of Some Perhydronaphthalenediol Monosulfonate Esters
  作者：Romano V. A. Orru、Joannes B. P. A. Wijnberg、Aede de Groot

  DOI：10.1021/jo00118a045

  日期：1995.6

  Substituent effects on the heterolysis of the perhydronaphthalene-1,4-diol monosulfonate esters 1, 7, and 8 induced by through-bond interactions (TBI) were studied. Evidence is found that, next to TBI, sigma-participation is the most important stereoelectronic effect which determines the reactivity of these compounds under strongly basic conditions in refluxing benzene. Substituents at carbon atoms adjacent to the carbon atom bearing the sulfonate ester group increase the contribution of a-participation which is expressed in a higher reactivity of these compounds. The product composition is primarily dependent on the degree of substitution at C(4). Homofragmentation and elimination are found when C(4) is unsubstituted as the reaction of mesylate 1 shows. Due to the repulsive 1,3-peri effect between the equatorial Me groups at C(4) and C(6) in the reaction of 7 and a combination of this 1,3-peri effect and the 4,4-dimethyl effect in that of 8, the ideal W arrangement is distorted. Consequently, no homofragmentation is observed with these compounds, and other reaction pathways (elimination, 1,3-H and 1,2-Me shifts) are now favored.