(1R*,2R*,11S*)-11-methyltricyclo<5.4.0.0^2,7>undec-7-en-3-one | 119986-84-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1R*,2R*,11S*)-11-methyltricyclo<5.4.0.0^2,7>undec-7-en-3-one
• 英文别名: (1R,2R,11S)-11-methyltricyclo[5.4.0.02,11]undec-7-en-3-one
• CAS: 119986-84-4
• 化学式: C₁₂H₁₆O
• 分子量: 176.258
• InChiKey: IOSVIRIXILAJEU-TUAOUCFPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1R*,2R*,11S*)-11-methyltricyclo<5.4.0.0^2,7>undec-7-en-3-one 在 sodium tetrahydroborate 、 lithium aluminium tetrahydride 、 四丙基高钌酸铵 、 4 A molecular sieve 、 magnesium 、 N-甲基吗啉氧化物 、 1,2-二溴乙烷 、 三乙胺 、 lithium hexamethyldisilazane 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 水 为溶剂， 反应 20.5h， 生成 (1R*,2R*,4S*,11S*)-4-<(1S*,3E)-1-<(tert-Butyldimethylsiloxy)methyl>-3-pentenyl>-11-methyltricyclo<5.4.0.0^2,11>undec-7-en-3-one
  参考文献：
  名称：

  Studies Directed toward the Total Synthesis of Cerorubenic Acid-III. 4. Exploration of an Organometallic Approach to Construction of the Eastern Sector

  摘要：

  The concept of an intramolecular organometallic approach to the most illustrious member of the cerorubenic acid family is outlined. Alkylation of ketone 2 with the ethyl iodoacetate and conversion of the resultant intermediate into lactone 9 provided a ready means for attaching side chains carrying a vinyl iodide substituent. Arrival at the key iodo ketones was next realized by a three-step sequence involving sodium borohydride reduction, regiocontrolled silylation of the primary hydroxyl group in the diol, and Dess-Martin oxidation. The crucial six-membered cyclization of these intermediates is not favored kinetically, and reductive deiodination was observed, if reaction occurred at all. Attempts to generate vinyl stannanes from these same substrates were also ineffective. The failure of this approach demonstrates the difficulties associated with closure of ring D, a phenomenon that has earlier been observed in the context of other exploratory routes to cerorubenic acid-III.

  DOI：

  10.1021/jo00120a026
• 作为产物：
  描述：

  3-methyl-3-vinylcyclohexan-1-one 在 六甲基磷酰三胺 、 正丁基锂 、 jones reagent 、 PPA 、 硼烷四氢呋喃络合物 、 氧气 、 三氯化铁 、 双(三甲基硅烷基)氨基钾 、 rose bengal 、 对甲苯磺酸 、 溶剂黄146 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 苯 为溶剂， 反应 38.09h， 生成 (1R*,2R*,11S*)-11-methyltricyclo<5.4.0.0^2,7>undec-7-en-3-one
  参考文献：
  名称：

  Studies directed toward the total synthesis of cerorubenic acid-III. 1. Expedient construction of the tetracyclic core by oxyanionic sigmatropy

  摘要：

  A synthesis of the ABCD ring framework of cerorubenic acid-III is described. Diketone 5 was first prepared by intramolecular oxidative coupling of the dienolate 10 and then suitably desymmetrized to deliver 15b. Anionic oxy-Cope rearrangement of this intermediate resulted in construction of 18, a ketone not only having all three contiguous stereogenic centers properly established but also equipped with adequate functionality for the further elaboration of ring D. In the present effort, this thrust took the form of homologation to 21, conversion to the activated diene 22, and Diels-Alder cycloaddition to methyl acrylate at high pressure. Once it became obvious that first-formed ketone 26 greatly preferred adoption of trans stereochemistry at the ring juncture, attempts to skirt this issue were made by preparing both 29 and 32. However, these advanced intermediates proved unresponsive to conjugate reduction, and attention was therefore redirected to alternative possible means for elaboration of the eastern sector.

  DOI：

  10.1021/jo00068a019

文献信息

• Rapid construction of the tetracyclic nucleus of cerorubenic acid-III by oxyanionic cope chemistry
  作者：Leo A. Paquette、Marc-André Poupart

  DOI：10.1016/s0040-4039(00)80072-6

  日期：1988.1

  Ketone 3, produced directly by anionic oxy-Cope rearrangement of 4, was crafted into silyloxydiene 8, Diels-Alder condensation of which with methyl acrylate under high pressure permitted arrival at 2, a tetracyclic precursor to cerorubenic acid-III.

  酮3，通过阴离子直接产生氧应对的重排4，被制作成silyloxydiene 8，第尔斯-阿尔德缩合，其在高压下与丙烯酸甲酯在到达允许2，四环前体cerorubenic酸III。
• Studies directed toward the total synthesis of cerorubenic acid-III. 2. Analysis of the inability to realize D ring formation by means of extraannular Robinson annulation
  作者：Leo A. Paquette、Gilbert Y. Lassalle、Carl J. Lovely

  DOI：10.1021/jo00068a020

  日期：1993.7

  The possibility of achieving construction of the complete framework of cerorubenic acid-III by means of a highly convergent anionic oxy-Cope steP followed by extraannular Robinson annulation has been probed. To this end, the dithiane 10 and iodides 14 were prepared and merged via S(N)2 chemistry. The dianion derived from 15d added smoothly to beta,gamma-unsaturated ketone 5, and the resulting diastereomers 18b and 19b were separated and individually transformed into the diketone pairs 22 and 23. When these advanced intermediates failed to undergo the cyclization required for assembly of ring D, the ability of parent ketone 28 to undergo nucleophilic addition with various of nucleophiles was assessed. Although somewhat attenuated, the carbonyl group in this peculiar structural setting gives evidence of being adequately reactive.