(1S,5R)-2-acetyl-8-azabicyclo<3.2.1>octa-2-ene | 172277-65-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,5R)-2-acetyl-8-azabicyclo<3.2.1>octa-2-ene
• 英文别名: (+)-norferruginine；(-)-Norferruginine；1-[(1S,5R)-8-azabicyclo[3.2.1]oct-2-en-2-yl]ethanone
• CAS: 172277-65-5
• 化学式: C₉H₁₃NO
• 分子量: 151.208
• InChiKey: DYSCFNKIZDWMSK-CBAPKCEASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  聚合甲醛 、 (1S,5R)-2-acetyl-8-azabicyclo<3.2.1>octa-2-ene 在 sodium cyanoborohydride 作用下， 以 乙腈 为溶剂， 反应 0.25h， 以97%的产率得到(+)-ferruginine
  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：

  (1R,4S,5S)-8-tert-butoxycarbonyl-4-(1'-hydroxyethyl)-8-azabicyclo[3.2.1]octan-3-one 在 三乙胺 咪唑 、 甲酸 、 potassium tert-butylate 、 四丁基氟化铵 、 palladium diacetate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三苯基膦 、 pyridinium chlorochromate 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 51.75h， 生成 (1S,5R)-2-acetyl-8-azabicyclo<3.2.1>octa-2-ene
  参考文献：
  名称：

  A new divergent synthesis of (+)- and (−)-ferruginine utilizing PLE-catalyzed asymmetric dealkoxycarbonylation

  摘要：

  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.

  DOI：

  10.1016/s0957-4166(02)00657-2

文献信息

• 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 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。
• 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.