(+/-)-silphinene | 74284-57-4

• 英文名称: (+/-)-silphinene
• 英文别名: silphinene
• CAS: 74284-57-4；75171-53-8；83057-81-2
• 化学式: C₁₅H₂₄
• 分子量: 204.356
• InChiKey: VHIAMHVUKUKCHP-KCGXDXBQSA-N

物化性质

• 沸点：
  253.2±7.0 °C(Predicted)
• 密度：
  0.94±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.42
• 重原子数：
  15.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  (3aR,6R,6aS)-6-(iodomethyl)-4,4-dimethyl-2,3,3a,5,6,6a-hexahydropentalen-1-one 在 吡啶 、 盐酸 、 氢氧化钾 、 copper(l) iodide 、 氯化亚砜 、 三氟化硼乙醚 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 间氯过氧苯甲酸 、 肼 、 三氯氧磷 作用下， 以 四氢呋喃 、 乙醚 、 水 为溶剂， 反应 2.0h， 生成 (+/-)-silphinene
  参考文献：
  名称：

  Total synthesis of (±)-silphinene

  摘要：

  DOI：

  10.1016/s0040-4039(00)81333-7

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).