(2-Benzyloxyimino-ethyl)-(4-oxo-butyl)-carbamic acid tert-butyl ester | 176718-78-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2-Benzyloxyimino-ethyl)-(4-oxo-butyl)-carbamic acid tert-butyl ester
• 英文别名: tert-butyl N-(4-oxobutyl)-N-[(2Z)-2-phenylmethoxyiminoethyl]carbamate
• CAS: 176718-78-8
• 化学式: C₁₈H₂₆N₂O₄
• 分子量: 334.415
• InChiKey: WKCJPYPAXDZGLU-ODLFYWEKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  24
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  68.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2-Benzyloxyimino-ethyl)-(4-oxo-butyl)-carbamic acid tert-butyl ester 在 platinum(IV) oxide 4-二甲氨基吡啶 、 氢氧化钾 、 偶氮二异丁腈 、 氢气 、 三正丁基氢锡 、 碳酸氢钠 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 、 水 、 苯 为溶剂， 反应 28.0h， 生成 (3R,4R)-3-(4-Benzyloxy-benzoylamino)-4-hydroxy-azepane-1-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  Total Synthesis of (−)-Balanol

  摘要：

  The efficient total synthesis of (-)-balanol, a potent inhibitor of the protein kinase C, is described. (-)-Balanol consists,of a chiral hexahydroazepine-containing fragment and a benzophenone fragment, both of which were prepared via novel synthetic routes. The hexahydroazepine fragment was prepared in racemic form through either Bu3SnH- or SmI2-promoted radical cyclization of oxime ethers 2ab intramolecularly connected with the formyl group. SmI2-promoted radical cyclization of 2b was found to be particularly successful in the selective synthesis of the seven-membered trans-amino alcohol 8b. Preparation of the enantiomerically pure hexahydroazepine-containing fragment was achieved through the enantioselective enzymatic acetylation of racemic alcohol 9, employing the immobilized lipase from Pseudomonas sp. The benzophenone fragment was prepared in short steps through a biomimetic oxidative anthraquinone ring cleavage starting from commercially available natural chrysophanic acid 15c. This reaction proceeded via [4 + 2]-cycloaddition of singlet oxygen to anthracene derivative 17c, followed by Baeyer-Villiger-type rearrangement of the resulting hydroperoxide to afford the benzophenone derivatives 22 and 23.

  DOI：

  10.1021/jo980208r
• 作为产物：
  描述：

  chloroacetaldehyde O-benzyloxime 在 吡啶 、 chromium(VI) oxide 、 sodium carbonate 作用下， 以 甲醇 、 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 7.25h， 生成 (2-Benzyloxyimino-ethyl)-(4-oxo-butyl)-carbamic acid tert-butyl ester
  参考文献：
  名称：

  Total Synthesis of (−)-Balanol

  摘要：

  The efficient total synthesis of (-)-balanol, a potent inhibitor of the protein kinase C, is described. (-)-Balanol consists,of a chiral hexahydroazepine-containing fragment and a benzophenone fragment, both of which were prepared via novel synthetic routes. The hexahydroazepine fragment was prepared in racemic form through either Bu3SnH- or SmI2-promoted radical cyclization of oxime ethers 2ab intramolecularly connected with the formyl group. SmI2-promoted radical cyclization of 2b was found to be particularly successful in the selective synthesis of the seven-membered trans-amino alcohol 8b. Preparation of the enantiomerically pure hexahydroazepine-containing fragment was achieved through the enantioselective enzymatic acetylation of racemic alcohol 9, employing the immobilized lipase from Pseudomonas sp. The benzophenone fragment was prepared in short steps through a biomimetic oxidative anthraquinone ring cleavage starting from commercially available natural chrysophanic acid 15c. This reaction proceeded via [4 + 2]-cycloaddition of singlet oxygen to anthracene derivative 17c, followed by Baeyer-Villiger-type rearrangement of the resulting hydroperoxide to afford the benzophenone derivatives 22 and 23.

  DOI：

  10.1021/jo980208r

文献信息

• A Novel and Chiral Synthesis of Both Enantiometers of trans-3-Amino-4-hydroxyhexahydroazepine, a Key Intermediate for the Synthesis of Balanol.
  作者：Takeaki NAITO、Mayumi TORIEDA、Kazumi TAJIRI、Ichiya NINOMIYA、Toshiko KIGUCHI

  DOI：10.1248/cpb.44.624

  日期：——

  Both enantiomers of the hexahydroazepine (7), key intermediates for the synthesis of (-)-balanol (1) and its enantiomer, were effectively synthesized via the shortest route involving stannyl radical cyclization of the aldehyde (4) connected with oxime ether followed by the optical resolution of the resulting azepine (7).

  六氢氮杂环庚烷（7）的两种对映体都是合成(-)-丙醇（1）及其对映体的关键中间体，它们都是通过最短的路线有效合成的，包括醛（4）与肟醚的链烷自由基环化，然后对生成的氮杂环庚烷（7）进行光学解析。