4-[(1R,3R,6S)-1,6-dimethyl-2-methylidene-3-(2-oxoethyl)cyclohexyl]butanenitrile | 150930-64-6

• 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: 4-[(1R,3R,6S)-1,6-dimethyl-2-methylidene-3-(2-oxoethyl)cyclohexyl]butanenitrile
• CAS: 150930-64-6
• 化学式: C₁₅H₂₃NO
• 分子量: 233.354
• InChiKey: NYAYRZMOLYUECC-NWANDNLSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  40.9
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-[(1R,3R,6S)-1,6-dimethyl-2-methylidene-3-(2-oxoethyl)cyclohexyl]butanenitrile 在 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 生成 (1R,3R,6S)-3-<(E)-5-(1,3-dioxolan-2-yl)-3-methyl-2-pentenyl>-1,6-dimethyl-2-methylenecyclohexanebutyronitrile
  参考文献：
  名称：

  Enantioselective synthesis of (+)-cleomeolide, the structurally unique diterpene lactone constituent of Cleome viscosa

  摘要：

  The first total synthesis of (+)-cleomeolide has been accomplished in enantioselective fashion from optically pure Wieland-Miescher ketone.

  DOI：

  10.1016/s0040-4039(00)73626-4
• 作为产物：
  描述：

  (4'aS)-4',4'a,7',8'-tetrahydro-4'a-methylspiro<1,3-dithiolane-2,2'(3'H)-naphthalen>-5'(6'H)-one 在 对甲苯磺酸 咪唑 、 盐酸 、 sodium tetrahydroborate 、 lithium aluminium tetrahydride 、 18-冠醚-6 、 水 、 mercury(II) trifluoroacetate 、 双(三甲基硅烷基)氨基钾 、 三乙基硼氢化锂 、 氟化氢吡啶 、 三乙胺 、 间氯过氧苯甲酸 、 thallium(III) nitrate 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 、 xylene 、 苯 为溶剂， 反应 3.0h， 生成 4-[(1R,3R,6S)-1,6-dimethyl-2-methylidene-3-(2-oxoethyl)cyclohexyl]butanenitrile
  参考文献：
  名称：

  Enantioselective synthesis of (+)-cleomeolide, the structurally unique diterpene lactone constituent of Cleome viscosa

  摘要：

  The first total synthesis of (+)-cleomeolide has been accomplished in enantioselective fashion from optically pure Wieland-Miescher ketone.

  DOI：

  10.1016/s0040-4039(00)73626-4

文献信息

• Total Synthesis of the Cembranoid Diterpene Lactone (+)-Cleomeolide. Some Remarkable Conformational Features of Nine-Membered Belts Linked in 2,6-Fashion to a Methylenecyclohexane Core
  作者：Leo A. Paquette、Ting-Zhong Wang、Christophe M. G. Philippo、Shaopeng Wang

  DOI：10.1021/ja00087a023

  日期：1994.4

  The total synthesis of (+)-cleomeolide (1) has been accomplished. The key construction elements of this cembranoid lactone were (i) improved conversion of optically pure Wieland-Miescher ketone into dienol ether 12 and oxidative cleavage of the latter to aldehydo ester 13; (ii) avoidance of complications arising from steric blockade of C-15 for introduction of the methylene group at that site; (iii) exploitation of an intramolecular Wadsworth-Emmons cyclization for macrocyclic ring construction; (iv) modulation of the conformation adopted by the medium ring by diastereofacial control of epoxidation of the C-3/C-4 double bond; and (v) intramolecular cyclization of the epoxy acid derived from 27 by nucleophilic capture at the more substituted oxiranyl carbon to deliver the target molecule. The deep-seated topographical change that accompanies the formation of 29 projects the macrocyclic ring quasi-axially from the methylenecyclohexane subunit in the manner known by X-ray crystallography to be adopted by the target compound. The intramolecular cyclization to set the bridgehead double bond was thereby facilitated.
• Enantioselective synthesis of (+)-cleomeolide, the structurally unique diterpene lactone constituent of Cleome viscosa
  作者：Leo A. Paquette、Wang Ting-Zhong、Shaopeng Wang、Christophe M.G. Philippo

  DOI：10.1016/s0040-4039(00)73626-4

  日期：1993.5

  The first total synthesis of (+)-cleomeolide has been accomplished in enantioselective fashion from optically pure Wieland-Miescher ketone.