15,16-Dimethoxy-6β-methoxycarbonyl-3,8-dioxo-Δ¹-erythrinan | 95456-70-5

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 刺桐生物碱
• 英文名称: 15,16-Dimethoxy-6β-methoxycarbonyl-3,8-dioxo-Δ¹-erythrinan
• 英文别名: methyl (4aS,13bR)-11,12-dimethoxy-2,6-dioxo-1,5,8,9-tetrahydroindolo[7a,1-a]isoquinoline-4a-carboxylate
• CAS: 95456-70-5
• 化学式: C₂₀H₂₁NO₆
• 分子量: 371.39
• InChiKey: UNBLJIUGDRZVPS-VQTJNVASSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  27
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  82.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  15,16-Dimethoxy-6β-methoxycarbonyl-3,8-dioxo-Δ¹-erythrinan 在 咪唑 sodium tetrahydroborate 、 cerium(III) chloride 、 3-乙基戊烷-3-硫醇 、 四丁基硫酸氢铵 、 sodium hydride 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 calcium chloride 作用下， 以 二甲基亚砜 、 苯 为溶剂， 反应 17.47h， 生成 3α,15,16-Trimethoxy-8-oxo-Δ¹-cis-erythrinan
  参考文献：
  名称：

  Synthesis of Erythrina and Related Alkaloids. XXIV. Total Synthesis of Erysotrine from 1,7-Cycloerythrinan Derivatives by the Use of a New 1,2-Carbonyl Transposition Method.

  摘要：

  处理2, 8-二氧代-1, 7-环赤霉烷与苯硒烯氯化物，在BF3·Et2O的催化下，得到3-氯-3-苯硒烯衍生物，通过3-苯硒烯衍生物进一步反应转变为Δ3-3-苯硒烯衍生物。无论是3-苯硒烯衍生物还是3-氯-3-苯硒烯衍生物，在与甲醇中的汞(II)高氯酸盐(MPC)处理时，均可得到3, 3-二甲氧基衍生物，从而提供了一种在原碳基团α位点引入掩蔽羰基的新方法。因此，1与苯硒烯氯化物在酸性条件下反应，然后在甲醇中进行MPC处理和硼氢化物还原，得到2α-羟基-3, 3-二甲氧基衍生物，产率为57%。该产物在四个步骤中转化为共轭酮，产率为72%。该化合物的羧甲氧基通过CaCl2-二甲基亚砜-3-乙基戊烷-3-硫醇法去除，得到烯酮4，产率为70-80%，并异构化为共轭酮25c，产率为100%。最终，该化合物在四个步骤中转化为天然的赤霉碱(±)-依索氨碱(5)，产率为31%，并进一步转化为(±)-依索丁(6)。

  DOI：

  10.1248/cpb.39.1365
• 作为产物：
  描述：

  在 咪唑 、 盐酸 、 三正丁基氢锡 、 sodium hydride 作用下， 以 丙酮 、 甲苯 为溶剂， 反应 3.0h， 生成 15,16-Dimethoxy-6β-methoxycarbonyl-3,8-dioxo-Δ¹-erythrinan
  参考文献：
  名称：

  α-苯基硒基酮新反应在赤藓碱合成中的应用

  摘要：

  在甲醇中用高氯酸汞（Ⅱ）处理α-苯基硒基酮，得到α，α-二甲氧基酮。通过使用该新反应，合成了赤藓素生物碱赤藓碱。

  DOI：

  10.1039/c39840001216

文献信息

• Application of a new reaction of α-phenylselenylketones to the synthesis of erysotrine
  作者：Yoshisuke Tsuda、Shinzo Hosoi、Akira Nakai、Takeshi Ohshima、Yuki Sakai、Fumiyuki Kiuchi

  DOI：10.1039/c39840001216

  日期：——

  Treatment of an α-phenylselenylketone with mercury(II) perchlorate in methanol yielded an α,α-dimethoxyketone; by using this new reaction an erythrinan alkaloid, erysotrine, was synthesized.

  在甲醇中用高氯酸汞（Ⅱ）处理α-苯基硒基酮，得到α，α-二甲氧基酮。通过使用该新反应，合成了赤藓素生物碱赤藓碱。
• A Triple Cascade Sequence as a Strategy for the Construction of the Erythrinane Skeleton
  作者：Albert Padwa、Rudiger Hennig、C. Oliver Kappe、Thomas S. Reger

  DOI：10.1021/jo9716183

  日期：1998.2.1

  alpha-Thiocarbocations generated from Pummerer reactions of several o-imido sulfoxides were intercepted by adjacent carbonyl groups to produce alpha-amido-substituted isobenzofurans as transient intermediates. When an olefinic tether was present, intramolecular Diels-Alder cycloaddition occurred followed by a ring-opening-elimination sequence that produced an N-acyliminium ion. Deprotonation of the iminium ion led to oxindole derivatives in good yields, When the iminium ion contained both a Mocking substituent, such as a carbomethoxy group, as a ell as an activated aromatic pi-tether, the N-acyliminium ion intermediate underwent stereoselective spirocyclization to afford cis-3,4-benzoerythrinane or homoerythrinane derivatives in good yield. The overall triple cascade sequence represents an efficient one-pot approach toward the erythrina skeleton in which the spirocyclic ABC skeleton is assembled in a single operation. The scope and limitations of the triple cascade were explored by varying both the olefinic and nucleophilic tethers. The required sulfoxide precursors for these Pummerer-induced transformations were easily synthesized starting from 2-[(ethylthio)methyl]benzoic acid. The tandem Pummerer/Diels-Alder/N-acyliminium ion cyclization was used for the synthesis of indoloisoquinoline 38. Since compound 38 was converted to 47 which, in turn, was transformed into erysotramidine (2), its preparation represents an extraordinarily facile, formal synthesis of this member of the Erythrina alkaloid family.
• Synthesis of Erythrina and Related Alkaloids. XXIV. Total Synthesis of Erysotrine from 1,7-Cycloerythrinan Derivatives by the Use of a New 1,2-Carbonyl Transposition Method.
  作者：Yoshisuke TSUDA、Shinzo HSOI、Akira NAKAI、Yuki SAKAI、Tomoko ABE、Yukari ISHI、Fumiyuki KIUCHI、Takehiro SANO

  DOI：10.1248/cpb.39.1365

  日期：——

  Treatment of 2, 8-dioxo-1, 7-cycloerythrinans with phenylselenenyl chloride in the presence of BF3·Et2O as a catalyst gave 3-chloro-3-phenylselenenyl derivaties through the 3-phenylselenenyl derivative, which changed into the Δ3-3-phenylselenenyl derivative on further reaction.Both the 3-phenylselenenyl and 3-chloro-3-phenylselenenyl derivatives gave the 3, 3-dimethoxy derivative on treatment with mercury (II) perchlorate (MPC) in methanol, thus providing a new method for introduction of a masked carbonyl group at the α-position to the original carbonyl group.Thus, the reaction of 1 with phenylselenenyl chloride under acidic conditions followed by MPC treatment in methanol and borohydride reduction gave the 2α-hydroxy-3, 3-dimethoxy derivative in 57% yield.This was converted to the conjugated ketone in four steps (72%).The carbomethoxy group of this compound was removed by the CaCl2-dimethyl sulfoxide-3-ethylpentane-3-thiol method to give the enone 4(70-80%) which isomerized to the conjugated ketone 25c(100%).This ws converted to a natural Erythrina alkaloid, (±)-erysotramidine (5), in four steps (31%), and thence to (±)-erosotrine (6).

  处理2, 8-二氧代-1, 7-环赤霉烷与苯硒烯氯化物，在BF3·Et2O的催化下，得到3-氯-3-苯硒烯衍生物，通过3-苯硒烯衍生物进一步反应转变为Δ3-3-苯硒烯衍生物。无论是3-苯硒烯衍生物还是3-氯-3-苯硒烯衍生物，在与甲醇中的汞(II)高氯酸盐(MPC)处理时，均可得到3, 3-二甲氧基衍生物，从而提供了一种在原碳基团α位点引入掩蔽羰基的新方法。因此，1与苯硒烯氯化物在酸性条件下反应，然后在甲醇中进行MPC处理和硼氢化物还原，得到2α-羟基-3, 3-二甲氧基衍生物，产率为57%。该产物在四个步骤中转化为共轭酮，产率为72%。该化合物的羧甲氧基通过CaCl2-二甲基亚砜-3-乙基戊烷-3-硫醇法去除，得到烯酮4，产率为70-80%，并异构化为共轭酮25c，产率为100%。最终，该化合物在四个步骤中转化为天然的赤霉碱(±)-依索氨碱(5)，产率为31%，并进一步转化为(±)-依索丁(6)。