(3R,4aR)-3-(tert-butyldimethylsiloxy)-4a-(1,1-dimethyl-2-propenyl)-1-(2-amino-2-oxoethyl)-9-oxy-2-oxo-2,3,4,4a,9-pentahydro-4aH-pyrido[2,3-b]indole | 1450816-02-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (3R,4aR)-3-(tert-butyldimethylsiloxy)-4a-(1,1-dimethyl-2-propenyl)-1-(2-amino-2-oxoethyl)-9-oxy-2-oxo-2,3,4,4a,9-pentahydro-4aH-pyrido[2,3-b]indole
• 英文别名: 2-[(3R,4aR)-3-[tert-butyl(dimethyl)silyl]oxy-4a-(2-methylbut-3-en-2-yl)-9-oxido-2-oxo-3,4-dihydropyrido[2,3-b]indol-9-ium-1-yl]acetamide
• CAS: 1450816-02-0
• 化学式: C₂₄H₃₅N₃O₄Si
• 分子量: 457.645
• InChiKey: FZZBOPBCMXSERP-HOYKHHGWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  32
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  101
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (3R,4aR)-3-(tert-butyldimethylsiloxy)-4a-(1,1-dimethyl-2-propenyl)-1-(2-amino-2-oxoethyl)-9-oxy-2-oxo-2,3,4,4a,9-pentahydro-4aH-pyrido[2,3-b]indole 在 四丁基氢氧化铵 、 sodium hydride 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 1.38h， 生成 (6R,7aR,12aR)-1-[[2-(trimethylsilyl)ethoxy]methyl]-6,12-(tert-butyldimethylsiloxy)-7a-(1,1-dimethyl-2-propenyl)-6,7,7a,12-tetraheydro-1H,5H-imidazo[1',2':1,2]pyrido[2,3-b]indole-2,5(3H)-dione
  参考文献：
  名称：

  Asymmetric Total Synthesis of Neoxaline

  摘要：

  A first asymmetric total synthesis and determination of the absolute configuration of neoxaline has been accomplished through the highly stereoselective introduction of a reverse prenyl group to create a quaternary carbon stereocenter using (-)-3a-hydroxyfuroindoline as a building block, construction of the indoline spiroaminal via cautious stepwise oxidations with cyclizations from the indoline, assembly of (Z)-dehydrohistidine, and photoisomerization of unnatural (Z)-neoxaline to the natural (E)-neoxaline as the key steps.

  DOI：

  10.1021/ja406657v
• 作为产物：
  描述：

  (2R,3aR,8aS)-2-(carbamoylmethylcarbamoyl)-8-hydro-3a-(1,1-dimethyl-2-propenyl)-2,3,3a,8a-tetrahydrofuro[2,3-b]indole 在 2,6-二甲基吡啶 、 sodium tungstate (VI) dihydrate 、 lead(IV) tetraacetate 、 过氧化脲素 、 三乙酰氧基硼氢化钠 、 溶剂黄146 作用下， 以 二氯甲烷 、 氯仿 、 1,2-二氯乙烷 为溶剂， 反应 8.92h， 生成 (3R,4aR)-3-(tert-butyldimethylsiloxy)-4a-(1,1-dimethyl-2-propenyl)-1-(2-amino-2-oxoethyl)-9-oxy-2-oxo-2,3,4,4a,9-pentahydro-4aH-pyrido[2,3-b]indole
  参考文献：
  名称：

  Asymmetric Total Synthesis of Neoxaline

  摘要：

  A first asymmetric total synthesis and determination of the absolute configuration of neoxaline has been accomplished through the highly stereoselective introduction of a reverse prenyl group to create a quaternary carbon stereocenter using (-)-3a-hydroxyfuroindoline as a building block, construction of the indoline spiroaminal via cautious stepwise oxidations with cyclizations from the indoline, assembly of (Z)-dehydrohistidine, and photoisomerization of unnatural (Z)-neoxaline to the natural (E)-neoxaline as the key steps.

  DOI：

  10.1021/ja406657v

文献信息

• Asymmetric Total Synthesis of Indole Alkaloids Containing an Indoline Spiroaminal Framework
  作者：Takeshi Yamada、Tetsuya Ideguchi-Matsushita、Tomoyasu Hirose、Tatsuya Shirahata、Rei Hokari、Aki Ishiyama、Masato Iwatsuki、Akihiro Sugawara、Yoshinori Kobayashi、Kazuhiko Otoguro、Satoshi Ōmura、Toshiaki Sunazuka

  DOI：10.1002/chem.201501150

  日期：2015.8.10

  of a reverse prenyl group to the congested benzylic carbon of furoindoline, a two‐pot transformation of indoline (containing three nitrogen atoms at appropriate positions) to the featured indoline spiroaminal framework, and elimination of carbonate assisted by the adjacent imidazole moiety to construct the (E)‐dehydrohistidine. The absolute stereochemistry of neoxaline was elucidated through our total

  吲哚生物碱，neoxaline，oxaline和meleagrin A的全部合成都包含独特的二氢吲哚螺环骨架，这是通过将反向异戊二烯基立体选择性地引入呋喃二氢吲哚的拥挤苄基碳中而完成的，这是吲哚的两锅法（在适当的二氢吲哚螺氨基骨架上在适当的位置包含三个氮原子），并通过相邻的咪唑部分协助消除碳酸根以构建（E）-脱氢组氨酸。通过我们的总合成可以阐明新氧沙林的绝对立体化学。此外，我们评估了新沙星和草酸星以及某些合成中间体的生物活性，尤其是抗感染特性。
• From Roquefortine C to Roquefortine L: Formation of a Complex Nitrone with Simple Oxidizing Agents
  作者：Claire M. Gober、Madeleine M. Joullié

  DOI：10.1002/ijch.201600107

  日期：2017.4

  The oxidation of roquefortine C to the nitrone roquefortine L was investigated using a number of different electrophilic oxidizing reagents. mCPBA and Oxone were shown to be the most effective in achieving this transformation, while unfavorable steric interactions precluded oxidation by bulky reagents such as Davis oxaziridine. Finally, each of the oxidants was shown to promote aromatic hydroxylation

  使用多种不同的亲电子氧化剂，研究了roquefortine C氧化为硝基roquefortine L的过程。米CPBA和过硫酸氢钾被证明是最有效地实现这种转变，而不利的空间相互作用由膨松试剂如戴维斯氧氮杂环丙烷氧化排除。最后，在合成硝酮官能团后，每种氧化剂均显示出促进芳族羟基化的作用。
• Asymmetric Total Synthesis of Neoxaline
  作者：Tetsuya Ideguchi、Takeshi Yamada、Tatsuya Shirahata、Tomoyasu Hirose、Akihiro Sugawara、Yoshinori Kobayashi、Satoshi O̅mura、Toshiaki Sunazuka

  DOI：10.1021/ja406657v

  日期：2013.8.28

  A first asymmetric total synthesis and determination of the absolute configuration of neoxaline has been accomplished through the highly stereoselective introduction of a reverse prenyl group to create a quaternary carbon stereocenter using (-)-3a-hydroxyfuroindoline as a building block, construction of the indoline spiroaminal via cautious stepwise oxidations with cyclizations from the indoline, assembly of (Z)-dehydrohistidine, and photoisomerization of unnatural (Z)-neoxaline to the natural (E)-neoxaline as the key steps.