O1-tert-butyl O3-methyl 2-acetonyl-3-(7-methoxy-1,3-benzodioxol-5-yl)pyrrolidine-1,3-dicarboxylate | 1216960-93-8

• 分子结构分类: 有机化合物 - 生物碱及其衍生物
• 英文名称: O1-tert-butyl O3-methyl 2-acetonyl-3-(7-methoxy-1,3-benzodioxol-5-yl)pyrrolidine-1,3-dicarboxylate
• 英文别名: 1-O-tert-butyl 3-O-methyl 3-(7-methoxy-1,3-benzodioxol-5-yl)-2-(2-oxopropyl)pyrrolidine-1,3-dicarboxylate
• CAS: 1216960-93-8
• 化学式: C₂₂H₂₉NO₈
• 分子量: 435.474
• InChiKey: XVHCZGAGNBKVIY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  31
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  101
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  O1-tert-butyl O3-methyl 2-acetonyl-3-(7-methoxy-1,3-benzodioxol-5-yl)pyrrolidine-1,3-dicarboxylate 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 生成 C₂₁H₂₅NO₇
  参考文献：
  名称：

  An oxidative coupling for the synthesis of arylated quaternary stereocentres and its application in the total synthesis of powelline and buphanidrine

  摘要：

  Catechol derivatives directly bonded to all-carbon quaternary stereocentres are prevalent in nature. An oxidative coupling strategy for the synthesis of this motif is described. Pivoting on the base-catalysed Michael addition of carbon-centred pro-nucleophiles to in situ generated ortho-benzoquinones, the method is broad in scope, high yielding and provides remarkably simple access to this challenging motif. The application of this methodology in the total synthesis of the crinane-type amaryllidaceae alkaloids (+/-)-powelline and (+/-)-buphanidrine is demonstrated and our efforts towards an enantioselective synthesis described. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.04.132
• 作为产物：
  描述：

  2-(三甲基硅氧基)丙烯 、 1-(tert-butyl) 3-methyl 2-acetoxy-3-(7-methoxybenzo[d][1,3]dioxol-5-yl)pyrrolidine-1,3-dicarboxylate 在 三氟化硼乙醚 、 水 作用下， 以 二氯甲烷 为溶剂， 以91%的产率得到O1-tert-butyl O3-methyl 2-acetonyl-3-(7-methoxy-1,3-benzodioxol-5-yl)pyrrolidine-1,3-dicarboxylate
  参考文献：
  名称：

  （±）-鲍威尔碱和（±）-丁香碱的全合成

  摘要：

  （±）-鲍威尔碱（13个线性步骤，总产率为6％）和（±）-布啡啶碱（14个线性步骤，总产率为6％）的总合成，并已使用一种新的方法制备了克力烷骨架。有机催化氧化偶合可以高产率直接构建关键的季碳-芳基键，从而可以快速进入目标生物碱。

  DOI：

  10.1021/ol1000654

文献信息

• Total Synthesis of (±)-Powelline and (±)-Buphanidrine
  作者：Katherine M. Bogle、David J. Hirst、Darren J. Dixon

  DOI：10.1021/ol1000654

  日期：2010.3.19

  The total synthesis of (±)-powelline (13 linear steps in an overall yield of 6%) and (±)-buphanidrine (14 linear steps and a 6% overall yield) and has been achieved using a novel approach to the crinane skeleton. An organocatalytic oxidative coupling allowed direct construction of the key quaternary carbon-to-aryl bond in high yield allowing rapid access to the target alkaloids.

  （±）-鲍威尔碱（13个线性步骤，总产率为6％）和（±）-布啡啶碱（14个线性步骤，总产率为6％）的总合成，并已使用一种新的方法制备了克力烷骨架。有机催化氧化偶合可以高产率直接构建关键的季碳-芳基键，从而可以快速进入目标生物碱。
• An oxidative coupling for the synthesis of arylated quaternary stereocentres and its application in the total synthesis of powelline and buphanidrine
  作者：Katherine M. Bogle、David J. Hirst、Darren J. Dixon

  DOI：10.1016/j.tet.2010.04.132

  日期：2010.8

  Catechol derivatives directly bonded to all-carbon quaternary stereocentres are prevalent in nature. An oxidative coupling strategy for the synthesis of this motif is described. Pivoting on the base-catalysed Michael addition of carbon-centred pro-nucleophiles to in situ generated ortho-benzoquinones, the method is broad in scope, high yielding and provides remarkably simple access to this challenging motif. The application of this methodology in the total synthesis of the crinane-type amaryllidaceae alkaloids (+/-)-powelline and (+/-)-buphanidrine is demonstrated and our efforts towards an enantioselective synthesis described. (C) 2010 Elsevier Ltd. All rights reserved.