(4aR)-2,4a-dimethyl-5-methylene-trans-octahydronaphthalen-1(2H)-one | 137822-35-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4aR)-2,4a-dimethyl-5-methylene-trans-octahydronaphthalen-1(2H)-one
• 英文别名: (2S,4aR,8aR)-2,4a-dimethyl-5-methylidene-3,4,6,7,8,8a-hexahydro-2H-naphthalen-1-one
• CAS: 137822-35-6
• 化学式: C₁₃H₂₀O
• 分子量: 192.301
• InChiKey: KBERMKSDOWOWPJ-GAFUQQFSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.77
• 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：

  (4aR)-2,4a-dimethyl-5-methylene-trans-octahydronaphthalen-1(2H)-one 在 sodium methylate 作用下， 以 甲醇 为溶剂， 生成 (2R,4aR,8aS)-2,4a-dimethyl-5-methyleneoctahydronaphthalen-1(2H)-one
  参考文献：
  名称：

  Use of the Me3Sn function as a readily removable ‘anchoring’ group in the synthesis of enantiomerically pure bicyclic alcohols and ketones

  摘要：

  Subjection of (5R, 6R)-(-)-3,6-dimethyl-5-trimethylstannyl-2-cyclohexen-1-one (11) to appropriate annulation sequences provides the cis-fused ketones 15, 20, and 21, which, upon reduction (Li, NH3, THF,t-BuOH) are converted smoothly into the enantiomerically pure bicyclic alcohols 16, 22, and 23, respectively. Compound 16 is readily transformed into the unichiral ketones 6 and 7.

  DOI：

  10.1016/s0040-4039(00)92348-7
• 作为产物：
  描述：

  (R)-5-methyl-cyclohex-2-enone 在 四丙基高钌酸铵 、 4 A molecular sieve 、 N-甲基吗啉氧化物 作用下， 以 二氯甲烷 为溶剂， 生成 (4aR)-2,4a-dimethyl-5-methylene-trans-octahydronaphthalen-1(2H)-one
  参考文献：
  名称：

  Use of the Me3Sn function as a readily removable ‘anchoring’ group in the synthesis of enantiomerically pure bicyclic alcohols and ketones

  摘要：

  Subjection of (5R, 6R)-(-)-3,6-dimethyl-5-trimethylstannyl-2-cyclohexen-1-one (11) to appropriate annulation sequences provides the cis-fused ketones 15, 20, and 21, which, upon reduction (Li, NH3, THF,t-BuOH) are converted smoothly into the enantiomerically pure bicyclic alcohols 16, 22, and 23, respectively. Compound 16 is readily transformed into the unichiral ketones 6 and 7.

  DOI：

  10.1016/s0040-4039(00)92348-7

文献信息

• Constructing Quaternary Stereogenic Centers Using Tertiary Organocuprates and Tertiary Radicals. Total Synthesis of <i>trans</i>-Clerodane Natural Products
  作者：Daniel S. Müller、Nicholas L. Untiedt、André P. Dieskau、Gregory L. Lackner、Larry E. Overman

  DOI：10.1021/ja512527s

  日期：2015.1.21

  A new concise construction of trans-clerodane diterpenoids is reported in which oxacyclic and trans-hydronaphthalene fragments are coupled, and the critical C9-quaternary carbon stereocenter formed stereoselectively, by 1,6-addition of a tertiary cuprate or a tertiary carbon radical to β-vinylbutenolide. This strategy is specifically illustrated by total syntheses of (-)-solidagolactone (4), (-)-16-hydroxycleroda-3

  报道了一种新的反式克罗丹二萜类化合物的简明结构，其中氧杂环和反式氢化萘片段偶联，并且通过叔铜酸盐或叔碳自由基的 1,6-加成立体选择性地形成了关键的 C9-季碳立体中心-乙烯基丁烯内酯。该策略通过 (-)-solidagolactone (4)、(-)-16-hydroxycleroda-3,13-dien-15,16-olide (5, PL3) 和 (-)-annonene 的全合成得到具体说明。 6).
• Total synthesis of cis-clerodane diterpenoids: (–)-agelasine A and (+)-(3R,4S,5R,8S,9R,10S)-3,4-epoxyclerod-13-en-15,16-olide
  作者：Edward Piers、M. Livain Breau、Yongxin Han、Guy L. Plourde、Wen-Lung Yeh

  DOI：10.1039/p19950000963

  日期：——

  The preparation of the enantiomerically homogeneous bicyclic iodide 26 and its use as a key intermediate for the total syntheses of the cis-clerodane diterpenoids (-)-agelasine A 5 and (+)-(3R,4S,5R,8S,9R,10S)-3,4-epoxyclerod-13-en-15,16-olide 6 are described.
• Total syntheses of the diterpenoids (−)-kolavenol and (−)-agelasine B
  作者：Edward Piers、Jacques Y. Roberge

  DOI：10.1016/s0040-4039(00)60896-1

  日期：1992.11

  The trans-clerodane diterpenoids (-)-kolavenol (2) and (-)-agelasine B (1) have been prepared from the enantiomerically pure decalone 3. The key steps of the syntheses involve the stereoselective alkylation of the nitrile 4 (to give 5), the efficient coupling of the iodides 10 and 11 to produce the clerodane skeleton 12, and the electrochemical reduction of 16 to provide (-)-1.