(-)-(1S)-suberosanone

• 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: (-)-(1S)-suberosanone
• 英文别名: Suberosanone；(1S,2R,5S,6S,9S)-2,9,11,11-tetramethyltricyclo[4.3.2.01,5]undecan-3-one
• 化学式: C₁₅H₂₄O
• 分子量: 220.355
• InChiKey: KHINYKJYBNWSSP-IAGXKZSMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  α-Terrecyclene 在 sodium hydroxide 、 四丙基高钌酸铵 、 硼烷四氢呋喃络合物 、 双氧水 、 N-甲基吗啉氧化物 作用下， 以 二氯甲烷 为溶剂， 反应 5.75h， 生成 (-)-(1S)-suberosanone
  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

• Suberosanes as Potential Antitumor Agents: First Enantioselective Total Synthesis of (1S)-Suberosanone and Configurational Assignment of Suberosenol A
  作者：Françoise Dumas、Mohammad Kousara、Franck Bideau、Rama Ibrahim、Angélique Ferry、Pierre-Etienne Venot、Camille Dejean、Joël Raingeaud、Joëlle Dubois、Pascal Retailleau

  DOI：10.1055/s-0035-1561430

  日期：——

  reason for which remains to be elucidated. The first enantioselective total syntheses of two marine sesquiterpenes, natural (1S)-suberosanone and (1S)-suberosenol A, are achieved leading to the assignment of the absolute configuration of natural suberosenol A. A new access to (1S)-suberosenone from a key tricyclic enone was also developed leading to an overall improvement of the synthesis, allowing an

  献给已故的让·安杰洛教授 抽象 实现了两个海洋倍半萜的第一个对映选择性全合成，天然（1 S）-suberosanone和（1 S）-suberosenol A，导致确定了天然Suberosenol A的绝对构型。获得了（1 S）-还开发了关键三环烯酮的亚硝基苯甲酸酯，从而导致合成的整体改进，从而为亚硝基苯甲酚A提供了有效的途径。高压不对称迈克尔加成反应和高效的三氟乙酸银介导的α-烷基化以形成环A完成了关键步骤的合成。遗憾的是，合成（1 S）-异戊烷酮未保留天然产物所显示的皮摩尔细胞毒性活性，其原因尚待阐明。 实现了两个海洋倍半萜的第一个对映选择性全合成，天然（1 S）-suberosanone和（1 S）-suberosenol A，导致确定了天然Suberosenol A的绝对构型。获得了（1 S）-还开发了关键三环烯酮的亚硝基苯甲酸酯，从而导致合成的整体改进，从而为亚硝基苯甲酚A提供了
• 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.
• 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).