(2R,3S,5R,7R,8S)-5-methyl-2-(2-methylsulfanyl-2-methylsulfinylethyl)-3-(naphthalen-2-ylmethoxy)-7-phenylmethoxy-8-(phenylmethoxymethyl)oxocane | 871912-49-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (2R,3S,5R,7R,8S)-5-methyl-2-(2-methylsulfanyl-2-methylsulfinylethyl)-3-(naphthalen-2-ylmethoxy)-7-phenylmethoxy-8-(phenylmethoxymethyl)oxocane
• CAS: 871912-49-1
• 化学式: C₃₈H₄₆O₅S₂
• 分子量: 646.912
• InChiKey: YEYFZHHZTIVULT-KREDQKSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  45
• 可旋转键数：
  14
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  98.5
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (2R,3S,5R,7R,8S)-5-methyl-2-(2-methylsulfanyl-2-methylsulfinylethyl)-3-(naphthalen-2-ylmethoxy)-7-phenylmethoxy-8-(phenylmethoxymethyl)oxocane 在 咪唑 、 三乙基硅烷 、 草酰氯 、 三氟甲磺酸三甲基硅酯 、 4-甲基苯磺酸吡啶 、 二甲基亚砜 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 2.42h， 生成
  参考文献：
  名称：

  Convergent synthesis of the IJKLM-ring part of ciguatoxin CTX3C

  摘要：

  Convergent synthesis of the IJKLM-ring part (2) of ciguatoxin CTX3C has been achieved from the I-ring and the L-ring parts (4 and 5) in total eight steps in 27% overall yield. The carbanion derived from 4, stabilized by a dimethyldithioacetal S-oxide group, was readily reacted with aldehyde 5 to give an adduct, which was facilely transformed into the corresponding alpha,epsilon-dihydroxy ketone 3. The JK-ring formation from 3 under reductive conditions followed by oxidative M-ring cyclization efficiently led to the pentacyclic ether 2. Improved synthesis of 6, a synthetic intermediate for 4, was also established. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2005.09.164
• 作为产物：
  描述：

  (2R,4aR,6S,7R,9S,10aS)-6-[[tert-butyl(diphenyl)silyl]oxymethyl]-9-methyl-2-phenyl-4,4a,6,7,8,9,10,10a-octahydro-[1,3]dioxino[5,4-b]oxocin-7-ol 在 2,6-二甲基吡啶 、 ethandithiol 、 lithium aluminium tetrahydride 、 三氯化铝 、 三氟化硼乙醚 、 potassium tert-butylate 、 四丁基氟化铵 、 sodium hexamethyldisilazane 、 4-甲基苯磺酸吡啶 、 四丁基碘化铵 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 苯 为溶剂， 反应 16.25h， 生成 (2R,3S,5R,7R,8S)-5-methyl-2-(2-methylsulfanyl-2-methylsulfinylethyl)-3-(naphthalen-2-ylmethoxy)-7-phenylmethoxy-8-(phenylmethoxymethyl)oxocane
  参考文献：
  名称：

  Convergent synthesis of the IJKLM-ring part of ciguatoxin CTX3C

  摘要：

  Convergent synthesis of the IJKLM-ring part (2) of ciguatoxin CTX3C has been achieved from the I-ring and the L-ring parts (4 and 5) in total eight steps in 27% overall yield. The carbanion derived from 4, stabilized by a dimethyldithioacetal S-oxide group, was readily reacted with aldehyde 5 to give an adduct, which was facilely transformed into the corresponding alpha,epsilon-dihydroxy ketone 3. The JK-ring formation from 3 under reductive conditions followed by oxidative M-ring cyclization efficiently led to the pentacyclic ether 2. Improved synthesis of 6, a synthetic intermediate for 4, was also established. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2005.09.164

文献信息

• An improved synthesis of the C42–C52 segment of ciguatoxin 3C
  作者：Takafumi Saito、Kenshu Fujiwara、Yusuke Sano、Takuto Sato、Yoshihiko Kondo、Uichi Akiba、Yusuke Ishigaki、Ryo Katoono、Takanori Suzuki

  DOI：10.1016/j.tetlet.2018.02.052

  日期：2018.4

  intermediate C42–C52 (L-ring) segment was problematic. Therefore, a new and improved procedure for the C42–C52 segment, having modified protecting groups, was developed. The new route includes a chirality transferring Ireland-Claisen rearrangement for the construction of the vicinal dimethyl branching at C47–48, a one-pot cyclization process for the establishment of the stereocenters at C45 and C46 as

  在我们先前报道的构建雪茄毒素3C（CTX3C）IJKLM环的方法中，中间C42–C52（L环）链段的冗长合成过程存在问题。因此，针对C42–C52片段开发了一种经过改进的新方法，该方法具有修饰的保护基。新路线包括手性转移爱尔兰-克莱森重排，用于在C47-48处建立邻位二甲基支化；一锅环化过程，用于在C45和C46处建立立体中心，以及γ-羟基δ-内酯框架对应于L环，以及布朗的不对称巴豆基硼酸酯，用于在C43和C44处安装立体中心。新的C42–C52片段已与先前报道的C32–C41（I形环）片段成功配对，以生产IJKLM环。
• Convergent synthesis of the IJKLM-ring part of ciguatoxin CTX3C
  作者：Daisuke Domon、Kenshu Fujiwara、Akio Murai、Hidethoshi Kawai、Takanori Suzuki

  DOI：10.1016/j.tetlet.2005.09.164

  日期：2005.11

  Convergent synthesis of the IJKLM-ring part (2) of ciguatoxin CTX3C has been achieved from the I-ring and the L-ring parts (4 and 5) in total eight steps in 27% overall yield. The carbanion derived from 4, stabilized by a dimethyldithioacetal S-oxide group, was readily reacted with aldehyde 5 to give an adduct, which was facilely transformed into the corresponding alpha,epsilon-dihydroxy ketone 3. The JK-ring formation from 3 under reductive conditions followed by oxidative M-ring cyclization efficiently led to the pentacyclic ether 2. Improved synthesis of 6, a synthetic intermediate for 4, was also established. (c) 2005 Elsevier Ltd. All rights reserved.