9,10-(methylenedioxy)-<3a-(3aα,11bβ,11cα)>-2,3,3a,4,5,7,11b,11c-octahydro-1H-pyrrolo-<3,2,1-d,e>phenanthridin-5-one | 65294-39-5

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 石蒜科生物碱
• 英文名称: 9,10-(methylenedioxy)-<3a-(3aα,11bβ,11cα)>-2,3,3a,4,5,7,11b,11c-octahydro-1H-pyrrolo-<3,2,1-d,e>phenanthridin-5-one
• 英文别名: (3aRS,11bRS,11cSR)-9,10-(methylenedioxy)-1,2,3,3a,4,5,11b,11c-octahydropyrrolo[3,2,1-de]phenanthridin-5-one；2,3,3a,4,7,12b-hexahydro-1H-[1,3]dioxolo[4,5-j]pyrrolo[3,2,1-de]phenanthridin-5(3a1H)-one；(1R,15R,19S)-5,7-dioxa-12-azapentacyclo[10.6.1.02,10.04,8.015,19]nonadeca-2,4(8),9-trien-13-one
• CAS: 65294-39-5；93527-80-1
• 化学式: C₁₆H₁₇NO₃
• 分子量: 271.316
• InChiKey: VRXBZRCDSOJASZ-RDGWCUKFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  20
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  9,10-(methylenedioxy)-<3a-(3aα,11bβ,11cα)>-2,3,3a,4,5,7,11b,11c-octahydro-1H-pyrrolo-<3,2,1-d,e>phenanthridin-5-one 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 以79%的产率得到(±)-α-lycorane
  参考文献：
  名称：

  乙二醛/硝基炔的不对称催化共轭加成反应：在（+）-α-环烷和手性β-炔酸合成中的应用

  摘要：

  乙醛向多共轭底物硝基二炔和亚硝基炔的催化对映体选择性共轭加成反应已通过有机催化完成。以中等至良好的产率和高对映选择性获得了各种官能化的1，3-烯炔和炔丙基化合物。共轭加成反应的合成效用已在（+）-α-二十二烷的简明全合成和手性β-炔酸的无金属合成中得到了强调。

  DOI：

  10.1021/ol501158b
• 作为产物：
  描述：

  3a,4,7,12b-tetrahydro-1H-[1,3]dioxolo[4,5-j]pyrrolo[3,2,1-de]phenanthridin-5(3a1H)-one 在 palladium 10% on activated carbon 、 氢气 作用下， 以 甲醇 为溶剂， 反应 5.0h， 以95%的产率得到9,10-(methylenedioxy)-<3a-(3aα,11bβ,11cα)>-2,3,3a,4,5,7,11b,11c-octahydro-1H-pyrrolo-<3,2,1-d,e>phenanthridin-5-one
  参考文献：
  名称：

  （±）-α-Lycorane和（±）-1-Deoxylycorine的总合成

  摘要：

  开发了新的合成路线，以合成（±）-α-lycorane和（±）-1-deoxylycorine。所述内切3,5-二溴-2-吡喃酮与苯乙烯型亲二烯体-cycloadduct提供的枢转中间体标题天然产物的合成。

  DOI：

  10.1021/ol303157b

文献信息

• A Short Synthesis of the Erythrina Skeleton and of (±)-α-Lycorane
  作者：Luis D. Miranda、Samir Z. Zard

  DOI：10.1021/ol025534e

  日期：2002.4.1

  [reaction: see text] A new nonchain 5-endo radical cyclization starting with xanthates was exploited in a short synthesis of (+/-)-alpha-lycorane and the erythrina ring system.

  [反应：见正文]在短时合成（+/-）-α-二十二烷和erythrina环系统中，开发了一种以黄药开始的新的非链式5-内基自由基环化反应。
• A synthesis of (±)-Δ2-α-Lycoren-7-one, the key intermediate for the total synthesis of (±)-lycorine
  作者：Bunsuke Umezawa、Osamu Hoshino、Shohei Sawaki、Haruki Sashida、Kazuhiko Mori、Yoshinori Hamada、Katsumi Kotera、Yoichi Iitaka

  DOI：10.1016/s0040-4020(01)91130-5

  日期：1984.1

  cyclohexanecarboxylic acid (10), both of which were prepared by the Diels-Alder reaction of 3,4-methylenedioxy - ω - nitrostyrene with butadiene and the Robinson annelation of 3,4-methyl- enedioxy - phenylpyruvic acid (9) with methyl vinyl ketone, respectively, 14a was converted into (±)Δ2-α-lycoren-7-one (22b), which has been transformed into (±)-lycorine (1) by Torssell

  由八氢菲咯啶-3-酮（8b）以从5-芳基-4-硝基环己烯（2）和1-羟基-2-开始的两种方法制得（±）-α-Lycoran-3,5-dione（14a）。芳基-5-氧代-环己烷甲酸（10），两者都是通过3,4-亚甲基二氧基-ω-硝基苯乙烯与丁二烯的Diels-Alder反应和3,4-甲基二烯二氧基-苯基丙酮酸的Robinson酸化反应制得的。 （9）与甲基乙烯基酮，分别14A转化为（±）Δ 2 -α-lycoren -7-酮（22B），它已被转化成（±）-lycorine（1）由Torssell
• Total synthesis of (±)-α-lycorane and 4,5-dehydroanhydrolycorine
  作者：James H. Rigby、Mary E. Mateo

  DOI：10.1016/0040-4020(96)00605-9

  日期：1996.8

  The total syntheses of (±)-α-lycorane and dehydroanhydrolycorine are described. The key intermediate in both approaches is the hydroindolone 5, prepared from the [1+4] cycloaddition reaction of 1-isocyanatocyclohexene and cyclohexyl isocyanide. Alkylation of 5 with arylbromide 6 afforded 7. Hydrolysis of enamide 7 followed by reduction of the resultant enol yielded 10 as a single diastereomer. Radical-based

  描述了（±）-α-二十二烷和脱氢脱水二十二烷的总合成。两种方法中的关键中间体是氢化吲哚酮5，它是由1-异氰酸根合环己烯和环己基异氰酸酯的[1 + 4]环加成反应制得的。5与芳基溴化物6烷基化得到7。烯酰胺7的水解，然后还原所得烯醇，得到10，为单一非对映异构体。对该中间体进行基于自由基的环化，得到11个具有必要的反式在环B和C之间进行高价融合。自由基脱氧，然后还原酰胺羰基官能团，得到（±）-α-二十二烷。同样，用6-（氯甲基）-5-碘-1,3-苯并二恶唑将5烷基化，得到14。采用Heck反应的Jeffery修饰的Pd（OAc）2处理14，得到四环9。水解9，然后用DDQ氧化，得到15。使用氢化铝锂还原该材料中的两个羰基官能团，得到4-羟基脱水氢化的鸟氨酸（16）。羟基的甲磺酰化导致快速，自发消除，从而生成脱水脱氢花椰菜碱。
• Is an Iodine Atom Almighty as a Leaving Group for Bu₃SnH-Mediated Radical Cyclization? The Effect of a Halogen Atom on the 5-Endo-trig Radical Cyclization of <i>N</i>-Vinyl-α-halo Amides
  作者：Osamu Tamura、Hana Matsukida、Atsushi Toyao、Yoshifumi Takeda、Hiroyuki Ishibashi

  DOI：10.1021/jo020007u

  日期：2002.8.1

  The effect of a halogen atom as a leaving group on Bu3SnH-mediated 5-endo-trig radical cyclization of N-(cyclohex-l-enyl) alpha-halo amides was examined. The cyclization of alpha-chloro amides occurred with a high degree of efficiency, whereas the corresponding alpha-iodo congeners gave only limited quantities of cyclization products. A detailed study revealed that these phenomena could be attributed to the initial conformations of alpha-halo amides. The cyclizing ability of alpha-iodo amides can be restored with Bu3SnCl or Bu3SnF as an additive. The cyclization of an alpha-iodo amide in the presence of Bu3SnF could be applied to a short-step synthesis of lycoranes featuring sequential 5-endo-trig and 6-endo-trig radical cyclizations.
• Asymmetric Catalytic Conjugate Addition of Acetaldehyde to Nitrodienynes/Nitroenynes: Applications to the Syntheses of (+)-α-Lycorane and Chiral β-Alkynyl Acids
  作者：Xue-Ling Meng、Teng Liu、Zhong-Wen Sun、Jin-Chen Wang、Fang-Zhi Peng、Zhi-Hui Shao

  DOI：10.1021/ol501158b

  日期：2014.6.6

  The catalytic enantioselective conjugate addition of acetaldehyde to polyconjugated substrates, nitrodienynes and nitroenynes, has been accomplished using organocatalysis. Various functionalized 1,3-enynes and propargylic compounds were obtained in moderate to good yields with high enantioselectivity. The synthetic utilities of the conjugate addition reactions have been highlighted in the concise total

  乙醛向多共轭底物硝基二炔和亚硝基炔的催化对映体选择性共轭加成反应已通过有机催化完成。以中等至良好的产率和高对映选择性获得了各种官能化的1，3-烯炔和炔丙基化合物。共轭加成反应的合成效用已在（+）-α-二十二烷的简明全合成和手性β-炔酸的无金属合成中得到了强调。