1-benzoyl-4,5-epoxy-1,2,2a,3,4,5-hexahydrobenzindole | 39890-59-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: 1-benzoyl-4,5-epoxy-1,2,2a,3,4,5-hexahydrobenzindole
• CAS: 39890-59-0；124578-75-2；124578-76-3
• 化学式: C₁₈H₁₅NO₂
• 分子量: 277.323
• InChiKey: GQKGAFVCSGNPJP-ISTRZQFTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.27
• 重原子数：
  21.0
• 可旋转键数：
  1.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  32.84
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1-benzoyl-4,5-epoxy-1,2,2a,3,4,5-hexahydrobenzindole 在 palladium on activated charcoal manganese(IV) oxide 、 氢氧化钾 、 sodium hydroxide 、 磷酸 、 氨 、 氢气 、 碘 、 potassium carbonate 、 钯 、 过碘酸 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 水 、 溶剂黄146 、 甲苯 、 乙腈 、 正丁醇 为溶剂， -10.0~100.0 ℃ 、101.33 kPa 条件下， 反应 71.5h， 生成 (4R)-4-(二丙基氨基)-1,3,4,5-四氢苯并[cd]吲哚-6-甲酰胺
  参考文献：
  名称：

  Synthetic Studies toward the Partial Ergot Alkaloid LY228729, a Potent 5HT_1A Receptor Agonist

  摘要：

  Synthetic studies on LY228729 (3) afforded two innovative approaches for the construction of this class of partial ergoline 5HT(1a) receptor agonists. The first synthesis is based upon a diastereoselective epoxidation of racemic olefin 5, followed by ring opening and covalent resolution to furnish the key amino alcohol 8. Aziridination of amino alcohol 8, with subsequent tandem hydrogenolysis of the benzylic aziridine and auxiliary bonds, provided access to the optically active primary amine 13. A novel catalytic carboxamidation reaction installed the requisite side chain, Alternatively, the chiral pool was drawn upon for the single stereogenic center by virtue of L-tryptophan, albeit by a more circuitous route than expected. L-Tryptophan was differentially protected and reduced to the indoline diastereomers 26a,b which were separated by fractional crystallization. The two indoline diastereoisomers were independently cyclized by a Friedel-Crafts protocol, which under thermodynamic control afforded enantiomeric ketones 30a. The ketone was deoxygenated with a two-step reduction protocol to intersect the initial route and complete the second total synthesis. The two routes offer complementary access to this exciting class of partial ergot alkaloids.

  DOI：

  10.1021/jo971256z
• 作为产物：
  描述：

  1-benzoyl-1,2,2a,3-tetrahydro-benz[cd]indole 在 间氯过氧苯甲酸 作用下， 以 氯仿 为溶剂， 反应 6.0h， 以97%的产率得到1-benzoyl-4,5-epoxy-1,2,2a,3,4,5-hexahydrobenzindole
  参考文献：
  名称：

  麦角灵合成中的非对映选择性：面部选择性环氧化

  摘要：

  1-苯甲酰基-1,2,2a，3-四氢苯并[ cd ]吲哚（4a）的环氧化反应采用间氯过苯甲酸，具有高的非对映异构选择性（de = 96％）和化学收率（97％）。这种选择性的基础是通过取代基效应来探究的，并扩展到了其他氧化介质。

  DOI：

  10.1016/s0040-4039(00)99288-8

文献信息

• The synthesis of (+)- and (−)-1-benzoyl-1,2,2a,3,4,5-hexahydrobenz[cd]indol-4-amine, and preparation of LY228729.
  作者：Michael J. Martinelli、M. Robert Leanna、David L. Varie、Barry C. Peterson、Thomas J. Kress、James P. Wepsiec、Vien V. Khau

  DOI：10.1016/s0040-4039(00)97303-9

  日期：——

  Racemic epoxide 5 was reacted with S-Phenylethylamine to afford diastereomers 6 and 7, from which amino alcohol 6 could be isolated directly. Aziridine formation and tandem-hydrogenolysis provided optically pure primary amine 2 (31% from racemic 4), which was further elaborated to LY228729 (15), an interesting 5HT1a receptor agonist.
• Stereoselective Epoxidations and Electrophilic Additions to Partial Ergot Alkaloids and Conformationally-Fixed Styrenes. Experimental and Theoretical Modeling Evidence for the Importance of Torsional Steering as a Stereocontrol Element
  作者：Michael J. Martinelli、Barry C. Peterson、Vien V. Khau、Darrell R. Hutchison、M. Robert Leanna、James E. Audia、James J. Droste、Yun-Dong Wu、K. N. Houk

  DOI：10.1021/jo00087a042

  日期：1994.4

  Partial ergot alkaloid substrates and related conformationally-fixed styrenes undergo epoxidation, osmium tetraoxide dihydroxylation, and hydrobromination with a level of stereoselectivity which cannot be explained by steric control but is consistent with electrophilic attack to minimize torsional strain. Force-field modeling is consistent with the importance of torsional steering as the dominant stereochemical control element.
• Synthetic Studies toward the Partial Ergot Alkaloid LY228729, a Potent 5HT_1A Receptor Agonist
  作者：M. A. Carr、P. E. Creviston、D. R. Hutchison、J. H. Kennedy、V. V. Khau、T. J. Kress、M. R. Leanna、J. D. Marshall、M. J. Martinelli、B. C. Peterson、D. L. Varie、J. P. Wepsiec

  DOI：10.1021/jo971256z

  日期：1997.12.1

  Synthetic studies on LY228729 (3) afforded two innovative approaches for the construction of this class of partial ergoline 5HT(1a) receptor agonists. The first synthesis is based upon a diastereoselective epoxidation of racemic olefin 5, followed by ring opening and covalent resolution to furnish the key amino alcohol 8. Aziridination of amino alcohol 8, with subsequent tandem hydrogenolysis of the benzylic aziridine and auxiliary bonds, provided access to the optically active primary amine 13. A novel catalytic carboxamidation reaction installed the requisite side chain, Alternatively, the chiral pool was drawn upon for the single stereogenic center by virtue of L-tryptophan, albeit by a more circuitous route than expected. L-Tryptophan was differentially protected and reduced to the indoline diastereomers 26a,b which were separated by fractional crystallization. The two indoline diastereoisomers were independently cyclized by a Friedel-Crafts protocol, which under thermodynamic control afforded enantiomeric ketones 30a. The ketone was deoxygenated with a two-step reduction protocol to intersect the initial route and complete the second total synthesis. The two routes offer complementary access to this exciting class of partial ergot alkaloids.
• Diastereoselectivity in ergoline synthesis: A face selective epoxidation
  作者：M.Robert Leanna、Michael J. Martinelli、David L. Varie、Thomas J. Kress

  DOI：10.1016/s0040-4039(00)99288-8

  日期：1989.1

  Epoxidation of 1-Benzoyl-1,2,2a,3-tetrahydrobenz[cd]indole (4a) proceeded smoothly with metachloroperbenzoic acid with high exo diastereoselectivity (de = 96%) and chemical yield (97%). The basis for this selectivity was probed with substituent effects, and was extended to other oxidation media.

  1-苯甲酰基-1,2,2a，3-四氢苯并[ cd ]吲哚（4a）的环氧化反应采用间氯过苯甲酸，具有高的非对映异构选择性（de = 96％）和化学收率（97％）。这种选择性的基础是通过取代基效应来探究的，并扩展到了其他氧化介质。