α-Terrecyclene | 142041-52-9

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: α-Terrecyclene
• CAS: 142041-52-9
• 化学式: C₁₅H₂₄
• 分子量: 204.356
• InChiKey: BTTKOGNDCXVJAF-GZCFXPHUSA-N

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

• 作为反应物：
  描述：

  α-Terrecyclene 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以86%的产率得到terrecyclene-2α,3α-epoxide
  参考文献：
  名称：

  Carbocationic Rearrangements of Silphinane Derivatives

  摘要：

  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).

  DOI：

  10.1021/jo971579v
• 作为产物：
  描述：

  silphin-1α-ol 在 lithium aluminium tetrahydride 、 氯化亚砜 、 四丙基高钌酸铵 、 4 Angstroems MS 、 N-甲基吗啉氧化物 作用下， 以 四氢呋喃 、 吡啶 、 二氯甲烷 、 苯 为溶剂， 反应 16.5h， 生成 α-Terrecyclene
  参考文献：
  名称：

  Carbocationic Rearrangements of Silphinane Derivatives

  摘要：

  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).

  DOI：

  10.1021/jo971579v

文献信息

• Solvolytic rearrangement of silphin-2.alpha.-yl methanesulfonate to .alpha.-terrecyclene: a probable biogenetic relationship between silphinene and quadrone
  作者：Michael Klobus、Lijuan Zhu、Robert M. Coates

  DOI：10.1021/jo00042a001

  日期：1992.7

  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.