(R)-3,5,6,8a-tetrahydro-5,5,8a-trimethyl-3-oxo-2-naphthaleneacetaldehyde 2-(dimethyl acetal) | 144492-74-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (R)-3,5,6,8a-tetrahydro-5,5,8a-trimethyl-3-oxo-2-naphthaleneacetaldehyde 2-(dimethyl acetal)
• 英文别名: (4aR)-3-(2,2-dimethoxyethyl)-4a,8,8-trimethyl-7H-naphthalen-2-one
• CAS: 144492-74-0
• 化学式: C₁₇H₂₄O₃
• 分子量: 276.376
• InChiKey: IYLFDELTYDICMP-QGZVFWFLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (R)-3,5,6,8a-tetrahydro-5,5,8a-trimethyl-3-oxo-2-naphthaleneacetaldehyde 2-(dimethyl acetal) 在 palladium on activated charcoal 叔丁基过氧化氢 、 sodium hydroxide 、 lithium aluminium tetrahydride 、 三氯化铝 、 三氟化硼乙醚 、 氢气 、 乙酸乙酯 、 二乙胺 作用下， 以 甲醇 、 乙醚 、 乙醇 、 二氯甲烷 为溶剂， 70.0 ℃ 、101.33 kPa 条件下， 反应 5.5h， 生成 (±)-pallescensin A
  参考文献：
  名称：

  Enantioselective construction of natural (+)-pallescensin A. A sigmatropic pathway to furanosesquiterpenes.

  摘要：

  Addition of the cerium reagent derived from 3-lithiofuran and anhydroUS CeCl3 to optically pure bicyclic ketone 2 affords alcohol 4 selectively. Anionic oxy-Cope rearrangement of 4 in hot diglyme results in conversion to keto aldehyde 6, a consequence of beta-elimination following upon the [3,3]sigmatropic event. Advantage was then taken of chemoselective acetalization and unidirectional introduction of an enone double bond. Regio- and stereoselective epoxidation of 8 was a prelude to formation of the furan ring by BF3.etherate-promoted cyclization. Once the carbonyl group was reduced with alane, catalytic hydrogenation in the presence of diethylamine gave the title compound. An alternative scheme involving silylation of the furan ring as a protective maneuver, while entirely workable, was both less direct and less efficient.

  DOI：

  10.1021/jo00052a026
• 作为产物：
  描述：

  (4aR,8aR)-3,4,4a,5,6,8a-hexahydro-5,5,8a-trimethyl-3-oxo-2-naphthaleneacetaldehyde 在 氯化铵 、 lithium diisopropyl amide 作用下， 反应 13.67h， 生成 (R)-3,5,6,8a-tetrahydro-5,5,8a-trimethyl-3-oxo-2-naphthaleneacetaldehyde 2-(dimethyl acetal)
  参考文献：
  名称：

  Enantioselective construction of natural (+)-pallescensin A. A sigmatropic pathway to furanosesquiterpenes.

  摘要：

  Addition of the cerium reagent derived from 3-lithiofuran and anhydroUS CeCl3 to optically pure bicyclic ketone 2 affords alcohol 4 selectively. Anionic oxy-Cope rearrangement of 4 in hot diglyme results in conversion to keto aldehyde 6, a consequence of beta-elimination following upon the [3,3]sigmatropic event. Advantage was then taken of chemoselective acetalization and unidirectional introduction of an enone double bond. Regio- and stereoselective epoxidation of 8 was a prelude to formation of the furan ring by BF3.etherate-promoted cyclization. Once the carbonyl group was reduced with alane, catalytic hydrogenation in the presence of diethylamine gave the title compound. An alternative scheme involving silylation of the furan ring as a protective maneuver, while entirely workable, was both less direct and less efficient.

  DOI：

  10.1021/jo00052a026

文献信息

• Enantioselective construction of natural (+)-pallescensin A. A sigmatropic pathway to furanosesquiterpenes.
  作者：Leo A. Paquette、Robert E. Maleczka

  DOI：10.1021/jo00052a026

  日期：1992.12

  Addition of the cerium reagent derived from 3-lithiofuran and anhydroUS CeCl3 to optically pure bicyclic ketone 2 affords alcohol 4 selectively. Anionic oxy-Cope rearrangement of 4 in hot diglyme results in conversion to keto aldehyde 6, a consequence of beta-elimination following upon the [3,3]sigmatropic event. Advantage was then taken of chemoselective acetalization and unidirectional introduction of an enone double bond. Regio- and stereoselective epoxidation of 8 was a prelude to formation of the furan ring by BF3.etherate-promoted cyclization. Once the carbonyl group was reduced with alane, catalytic hydrogenation in the presence of diethylamine gave the title compound. An alternative scheme involving silylation of the furan ring as a protective maneuver, while entirely workable, was both less direct and less efficient.