(-)-epilupinine | 112065-89-1

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 羽扇豆生物碱
• 英文名称: (-)-epilupinine
• 英文别名: rac-(1S,9aR)-Octahydro-2H-quinolizin-1-ylmethanol；[(1R,9aS)-2,3,4,6,7,8,9,9a-octahydro-1H-quinolizin-1-yl]methanol
• CAS: 112065-89-1
• 化学式: C₁₀H₁₉NO
• 分子量: 169.267
• InChiKey: HDVAWXXJVMJBAR-UWVGGRQHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  23.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  乙酰氯 、 (-)-epilupinine 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 生成 (5R,6S)-1-aza-5-(acetoxymethyl)bicyclo<4.4.0>decane
  参考文献：
  名称：

  Highly diastereoselective alkylation of chiral tin(II) enolates onto cyclic acyl imines. An efficient asymmetric synthesis of bicyclic alkaloids bearing a nitrogen atom ring juncture

  摘要：

  DOI：

  10.1021/jo00291a012
• 作为产物：
  描述：

  6-乙氧基哌啶-2-酮 在 N-乙基哌啶 、 lithium aluminium tetrahydride 、 tin(II) trifluoromethanesulfonate 作用下， 以 四氢呋喃 为溶剂， 反应 56.08h， 生成 (-)-epilupinine
  参考文献：
  名称：

  Highly diastereoselective alkylation of chiral tin(II) enolates onto cyclic acyl imines. An efficient asymmetric synthesis of bicyclic alkaloids bearing a nitrogen atom ring juncture

  摘要：

  DOI：

  10.1021/jo00291a012

文献信息

• Organocatalytic Asymmetric Mannich Cyclization of Hydroxylactams with Acetals: Total Syntheses of (−)-Epilupinine, (−)-Tashiromine, and (−)-Trachelanthamidine
  作者：Dipankar Koley、Yarkali Krishna、Kyatham Srinivas、Afsar Ali Khan、Ruchir Kant

  DOI：10.1002/anie.201407185

  日期：2014.11.24

  cyclization between a hydroxylactam and acetal is described to provide fused, bicyclic alkaloids bearing a bridgehead N atom. Both aliphatic and aromatic substrates were used in this transformation to furnish chiral pyrrolizidinone, indolizidinone, and quinolizidinone derivatives in up to 89 % yield and 97 % ee. The total syntheses of (−)‐epilupinine, (−)‐tashiromine, and (−)‐trachelanthamidine also

  羟基内酰胺和乙缩醛之间的不对称有机催化单锅曼尼希环化反应可提供带有桥头N原子的稠合双环生物碱。脂肪族和芳香族底物均用于该转化中，以高达89％的收率和97％的ee值提供手性吡咯烷酮，吲哚啶酮和喹喔啉酮衍生物。（-）-癫痫素，（-）-tashiromine和（-）-trachelanthamidine的总合成也证明了该方法的普遍性。
• Asymmetric Total Synthesis of (-)-Lupinine and (+)-Epilupinine via α-Sulfinyl Ketimine. Stereocontrolled Reduction of β-Sulfinyl Enamines
  作者：Duy H. Hua、Shou Wu Miao、Ana A. Bravo、Dolores J. Takemoto

  DOI：10.1055/s-1991-26620

  日期：——

  (-)-Lupinine and (+)-epilupinine [(1R,9aR)- and (1S, 9aR)-octahydro-1-hydroxymethyl-2H-quinolizine] were synthesized from (+)-2,3,4,5-tetrahydro-6-[(R)-(4-methylphenyl)sulfinylmethyl]pyridine (4) in five steps. The intermediate, 3,4,6,7,8,9-hexahydro-1-[(R)-(4-methylphenyl)sulfinyl]-2H-quinolizine (7), was stereoselectively reduced with cerium(III) chloride heptahydrate and sodium borohydride to give predominantly C-9a-R isomers, (9aR)-octahydro-1-[(R)-(4-methylphenyl)sulfinyl]-2H-quinolizines.

  (-)-Lupinine 和 (+)-epilupinine [(1R,9aR)- 和 (1S,9aR)-八氢-1-羟甲基-2H-喹嗪]通过五步反应从 (+)-2,3,4,5-四氢-6-[(R)-(4-甲基苯基)亚砜甲基]吡啶 (4) 合成得到。中间体，3,4,6,7,8,9-六氢-1-[(R)-(4-甲基苯基)亚砜]-2H-喹嗪 (7)，经铈(III)氯化物七水合物和硼氢化钠选择性还原，主要得到 C-9a-R 异构体，即 (9aR)-八氢-1-[(R)-(4-甲基苯基)亚砜]-2H-喹嗪。
• Double Ring-Closing Metathesis Reaction of Nitrogen-Containing Tetraenes: Efficient Construction of Bicyclic Alkaloid Skeletons and Synthetic Application to Four Stereoisomers of Lupinine and Their Derivatives
  作者：Shengming Ma、Bukuo Ni

  DOI：10.1002/chem.200305581

  日期：2004.7.5

  The double ring-closing metathesis reaction of nitrogen-containing tetraenes was studied. The selectivity of the fused/dumbbell-type products can be controlled by the electronic/steric effects of the substituents attached to the C[double bond]C bonds and the s-cis/s-trans conformational ratios of the substrates. This methodology has also been successfully applied to the enantioselective synthesis of

  研究了含氮四烯的双环复分解反应。稠合/哑铃型产物的选择性可以通过连接于C [双键] C键的取代基的电子/立体效应和底物的s-顺式/ s-反式构象比来控制。该方法也已成功地应用于羽扇豆碱及其衍生物的四种立体异构体的对映选择性合成。
• A Concise Asymmetric Total Synthesis of (+)-Epilupinine
  作者：Tomohiro Tsutsumi、Sangita Karanjit、Atsushi Nakayama、Kosuke Namba

  DOI：10.1021/acs.orglett.9b00607

  日期：2019.4.19

  Asymmetric total synthesis of (+)-epilupinine was achieved in just three steps using only commercially available common reagents. The total synthesis involved alkylations of N-nosylamide, ozone oxidation, and sequential reactions of the removal of the nosyl group, intramolecular dehydrative condensation, intramolecular Mannich reaction catalyzed by l-proline, and a reduction.

  仅使用市售通用试剂，仅需三个步骤即可实现（+）-艾比卢皮碱的不对称全合成。总的合成涉及N-烷基酰胺的烷基化，臭氧氧化，以及去除烷基的顺序反应，分子内脱水缩合，1-脯氨酸催化的分子内曼尼希反应和还原。
• A short, enantioselective synthesis of (−)-epilupinine from proline via a spirocyclic ammonium ylide
  作者：B.N. Naidu、F.G. West

  DOI：10.1016/s0040-4020(97)01037-5

  日期：1997.12

  quinolizidine 8b with high diastereoselectivity (19:1 8b/7b) and in surprisingly high enantiomeric excess (75%). The key step presumably occurs via spirocyclic ylide 6b, which undergoes [1,2]-shift with retention. Rearrangement product 8b was converted to (−)-epilupinine 2 via an efficient, 3-step sequence.

  重氮酮5B，在从脯氨酸苄酯一步可用，后行转化为喹8B具有高非对映选择性（19：1的8b / 7B）和令人惊奇的高对映体过量（75％）。关键步骤大概是通过螺环内酯6b发生的，螺环内含物经历[1,2]移位。重排产物8b通过有效的3步序列转化为（-）-癫痫碱2。