(1S,5R)-2-acetyl-8-<(1,1-dimethylethoxy)carbonyl>-8-azabicyclo<3.2.1>octa-2-ene | 172172-48-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (1S,5R)-2-acetyl-8-<(1,1-dimethylethoxy)carbonyl>-8-azabicyclo<3.2.1>octa-2-ene
• 英文别名: (1S,5S)-2-acetyl-8-(tert-butoxycarbonyl)-8-azabicyclo<3.2.1>-2-octene；tert-butyl (1S,5R)-2-acetyl-8-azabicyclo[3.2.1]oct-2-ene-8-carboxylate；(1R,5S)-4-acetyl-8-tert-butoxycarbonyl-8-azabicyclo[3.2.1]oct-3-ene；(+)-(1S,5R)-N-Boc-norferruginine
• CAS: 172172-48-4
• 化学式: C₁₄H₂₁NO₃
• 分子量: 251.326
• InChiKey: VNFKXJBTBWRZAD-JQWIXIFHSA-N

物化性质

• 沸点：
  360.9±42.0 °C(Predicted)
• 密度：
  1.123±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1S,5R)-2-acetyl-8-<(1,1-dimethylethoxy)carbonyl>-8-azabicyclo<3.2.1>octa-2-ene 在 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以93%的产率得到(1S,5R)-2-acetyl-8-azabicyclo<3.2.1>octa-2-ene
  参考文献：
  名称：

  简明的不对称路线，使用烯环闭合复分解法连接到桥接的双环烷烃生物碱铁。

  摘要：

  [反应：见文本] Enyne复分解已被用于制备桥连的氮杂双环，并用于短暂的不对称合成的托帕烷铁精氨酸。事实证明，Grubbs第一代催化剂在烯炔复分解反应中优于第二代催化剂。

  DOI：

  10.1021/ol049665m
• 作为产物：
  描述：

  tert-butyl (2R,5S)-2-allyl-5-ethynyl-1-pyrrolidinecarboxylate 在 Grubbs catalyst first generation air 、 copper dichloride 、 palladium dichloride 作用下， 以 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 16.0h， 生成 (1S,5R)-2-acetyl-8-<(1,1-dimethylethoxy)carbonyl>-8-azabicyclo<3.2.1>octa-2-ene
  参考文献：
  名称：

  简明的不对称路线，使用烯环闭合复分解法连接到桥接的双环烷烃生物碱铁。

  摘要：

  [反应：见文本] Enyne复分解已被用于制备桥连的氮杂双环，并用于短暂的不对称合成的托帕烷铁精氨酸。事实证明，Grubbs第一代催化剂在烯炔复分解反应中优于第二代催化剂。

  DOI：

  10.1021/ol049665m

文献信息

• Formal Synthesis of (+)- and (–)-Ferruginine
  作者：Riccardo Piccardi、Philippe Renaud

  DOI：10.1002/ejoc.200700427

  日期：2007.10

  commercially available tropinone is reported. The desymmetrization of tropinone was achieved through formation of diastereomeric unsaturated sulfoxides using the Andersen procedure. Introduction of the acetyl C(2) side chain was achieved by conjugate addition of lithiated ethyl vinyl ether to an unsaturated sulfone. N-Boc-Norferruginine, an advanced intermediate for the synthesis of ferruginine, was prepared

  据报道，从市售的托品酮开始，天然存在的 (+)-铁蛋白及其对映异构体的正式合成。托品酮的去对称化是通过使用安德森程序形成非对映异构不饱和亚砜来实现的。乙酰基 C(2) 侧链的引入是通过将锂化乙基乙烯基醚共轭添加到不饱和砜来实现的。N-Boc-Norferruginine 是一种用于合成铁蛋白碱的高级中间体，分六步制备，总产率为 19%。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
• Enantiospecific Synthesis of (+)- and (−)-Ferruginine from <scp>l</scp>-Glutamic Acid. Synthesis of Tropanes <i>via</i> Intramolecular Iminium Ion Cyclization
  作者：Andrés S. Hernández、Adrian Thaler、Josep Castells、Henry Rapoport

  DOI：10.1021/jo9515081

  日期：1996.1.1

  Iminium ions, generated by decarbonylation of N-benzyl-5-[1-(methoxycarbonyl)-4-oxopentyl]-prolines, prolines, undergo intramolecular cyclization to afford 2,4-disubstituted tropanes in good yields. This transformation is also shown to be a stereospecific reaction. The value of these substituted tropanes has been demonstrated by functional group manipulation, leading to the enantiospecific synthesis of (+)-ferruginine, an alkaloid isolated from Darlinga ferruginea, and its unnatural enantiomer, (-)-ferruginine.
• Enantioselective Synthesis of Functionalized Tropanes by Rhodium(II) Carboxylate-Catalyzed Decomposition of Vinyldiazomethanes in the Presence of Pyrroles
  作者：Huw M. L. Davies、Julius J. Matasi、L. Mark Hodges、Nicholas J. S. Huby、Craig Thornley、Norman Kong、Jeffrey H. Houser

  DOI：10.1021/jo961920w

  日期：1997.2.1

  A series of enantiomerically enriched tropanes was synthesized by the rhodium(II) octanoate-catalyzed reaction of various N-BOC-protected pyrroles with vinyldiazomethanes. The overall 3 + 4 annulation occurs by a tandem cyclopropanation/Cope rearrangement. Asymmetric induction was best achieved in these transformations by using either (S)-lactate or (R)-pantolactone as a chiral auxiliary on the vinyldiazomethanes. Reactions carried out with the chiral catalyst tetrakis[N-( 4-tert-butylbenzenesulfonyl)-(L)-prolinato]dirhodium (2) provided moderate asymmetric induction, but also resulted in the formation of isomeric azabicyclooctane side products. The utility of the synthetic process was demonstrated through the asymmetric synthesis of(-)-anhydroecgonine methyl ester and (-)-ferruginine.
• A new divergent synthesis of (+)- and (−)-ferruginine utilizing PLE-catalyzed asymmetric dealkoxycarbonylation
  作者：Takahiro Katoh、Kiyoshi Kakiya、Takashi Nakai、Soichi Nakamura、Kiyoharu Nishide、Manabu Node

  DOI：10.1016/s0957-4166(02)00657-2

  日期：2002.10

  A new divergent synthesis of (+)- and (-)-ferruginine 4, via the optically active 8-benzyl-3-oxo-8-azabicy-clo[3.2.1]octane-2-carboxylates 6 is described. The P-keto ester intermediates 6 were prepared by a novel PLE-catalyzed asymmetric dealkoxycarbonylation of the symmetric tropinone-type diesters 5. The key problem in the synthesis is controlling the regioselectivity of the reaction at the 2- and 4-positions in the tropane framework of the P-keto ester 6 for introduction of the acetyl group. (C) 2002 Elsevier Science Ltd. All rights reserved.
• A Concise Asymmetric Route to the Bridged Bicyclic Tropane Alkaloid Ferruginine Using Enyne Ring-Closing Metathesis
  作者：Varinder K. Aggarwal、Christopher J. Astle、Mark Rogers-Evans

  DOI：10.1021/ol049665m

  日期：2004.4.1

  [reaction: see text] Enyne metathesis has been used to prepare bridged azabicycles and applied in a short asymmetric synthesis of the tropane ferruginine. A Grubbs first generation catalyst proved to be superior to the second generation catalyst in the enyne metathesis reaction.

  [反应：见文本] Enyne复分解已被用于制备桥连的氮杂双环，并用于短暂的不对称合成的托帕烷铁精氨酸。事实证明，Grubbs第一代催化剂在烯炔复分解反应中优于第二代催化剂。