2αH-terrecyclan-3α-ol | 142041-54-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 2αH-terrecyclan-3α-ol
• CAS: 142041-54-1
• 化学式: C₁₅H₂₆O
• 分子量: 222.371
• InChiKey: BDLGBFIOPGGWIN-JVFXBBKESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.47
• 重原子数：
  16.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  2αH-terrecyclan-3α-ol 在 四丙基高钌酸铵 、 N-甲基吗啉氧化物 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以96%的产率得到(-)-(1S)-suberosanone
  参考文献：
  名称：

  Solvolytic rearrangement of silphin-2.alpha.-yl methanesulfonate to .alpha.-terrecyclene: a probable biogenetic relationship between silphinene and quadrone

  摘要：

  The solvolytic rearrangement of silphin-2-alpha-yl methanesulfonate (4b) to tricyclic olefin 5 named alpha-terrecyclene suggests the occurrence of similar rearrangements in the biosynthesis of quadrone and its Aspergillus terreus co-metabolites.

  DOI：

  10.1021/jo00042a001
• 作为产物：
  描述：

  silphin-2α-yl methanesulfonate 在 sodium hydroxide 、 甲酸 、 硼烷 、 双氧水 、 sodium formate 作用下， 反应 3.75h， 生成 2αH-terrecyclan-3α-ol
  参考文献：
  名称：

  Solvolytic rearrangement of silphin-2.alpha.-yl methanesulfonate to .alpha.-terrecyclene: a probable biogenetic relationship between silphinene and quadrone

  摘要：

  The solvolytic rearrangement of silphin-2-alpha-yl methanesulfonate (4b) to tricyclic olefin 5 named alpha-terrecyclene suggests the occurrence of similar rearrangements in the biosynthesis of quadrone and its Aspergillus terreus co-metabolites.

  DOI：

  10.1021/jo00042a001

文献信息

• Carbocationic Rearrangements of Silphinane Derivatives
  作者：Robert M. Coates、Jonathan Z. Ho、Michael Klobus、Lijuan Zhu

  DOI：10.1021/jo971579v

  日期：1998.12.1

  Solvolysis of silphin-1 alpha and -1 beta-yl mesylates (18 alpha-OMs and 18 beta-OMs) gave rise to mixtures of silphinene (4), bridgehead alcohol 22-OH (or its acetate), and alpha-terrecyclene (5) accompanied by trace amounts of isocomene (1) and modhephene (2). The 10(3) higher solvolysis rate determined for 18 alpha-OMs over its epimer signifies a concerted rearrangement to a more stable tertiary bridgehead carbocation (36) which undergoes a second rearrangement and elimination to alpha-terrecyclene (5) (see Scheme 5 in the paper). Isocomene and modhephene presumably arise from a minor competing pathway resulting from 7-->1 hydride shift to the silphin-7-yl ion (38 = 11) which partitions between methyl and cyclopentane ring rearrangements. Acetolysis of secosilphinyl nosylate 21 (X = ONs) is accompanied by pi participation leading directly to 38 and from there to a 2:1 mixture (6%) of isocomene and modhephene. TiCl4-mediated heterolysis of silphin-1 alpha-yl trifluoroacetate (18 alpha-O2CCF3) initiates a complex rearrangement pathway to 3-chloro-1,4,4,11-tetramethyltricyclo[5.3.1.0(3,8)]undecane (24). alpha-Terrecyclene (5) was converted to various oxygenated terrecyclane derivatives by dihydroxylation, hydroboration, and epoxidation (see Scheme 3 in the paper) and to its exocyclic isomer beta-terrecyclene (34, see Scheme 4 in the paper). The observed rearrangements of the silphinyl mesylates (see Scheme 5 in the paper) afford chemical precedent for a biogenetic pathway that links terrecyclanes (e.g. quadrone), isocomene, and modhephene to the silphinane family of cyclopentanoid sesquiterpenes formally derivable from caryophyllene (see Scheme 1 in the paper).