(S)-2-[4-(tert-Butyl-diphenyl-silanyloxy)-butyl]-2,5-dihydro-pyrrole-1-carboxylic acid tert-butyl ester | 920749-74-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯啉
• 英文名称: (S)-2-[4-(tert-Butyl-diphenyl-silanyloxy)-butyl]-2,5-dihydro-pyrrole-1-carboxylic acid tert-butyl ester
• 英文别名: tert-butyl (2S)-2-[4-[tert-butyl(diphenyl)silyl]oxybutyl]-2,5-dihydropyrrole-1-carboxylate
• CAS: 920749-74-2
• 化学式: C₂₉H₄₁NO₃Si
• 分子量: 479.735
• InChiKey: BRZDOYZHUJNFSM-DEOSSOPVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.91
• 重原子数：
  34
• 可旋转键数：
  11
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.48
• 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：

  (S)-2-[4-(tert-Butyl-diphenyl-silanyloxy)-butyl]-2,5-dihydro-pyrrole-1-carboxylic acid tert-butyl ester 在 Oxone 、 edetate disodium 、 碳酸氢钠 作用下， 以 乙腈 为溶剂， 反应 18.5h， 以89%的产率得到
  参考文献：
  名称：

  手性烯丙基叠氮化物的空间偏向3,3-Sigmatropic重排：在生物碱的总合成中的应用

  摘要：

  We describe a tandem Mitsunobu/3,3-sigmatropic rearrangement of allylic azides on a chiral auxiliary system that favors one regioisomer thanks to its exceptional steric bias. The sequence may be completed by the oxidative cleavage of the auxiliary or by a ring-closing metathesis reaction that produces a carboor heterocycle directly and a recyclable form of the chiral auxiliary. Applications of the methodology to the total synthesis of (+)-coniine, (+)-lentiginosin, and (+)-pumiliotoxin C are reported.

  DOI：

  10.1021/jo800817p
• 作为产物：
  描述：

  (E)-tert-butyl(6-iodohex-5-en-1-yloxy)diphenylsilane 在 Grubbs catalyst first generation lithium aluminium tetrahydride 、 正丁基锂 、 迭氮酸 、 potassium carbonate 、 三乙胺 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 、 Petroleum ether 、 苯 为溶剂， 反应 69.5h， 生成 (S)-2-[4-(tert-Butyl-diphenyl-silanyloxy)-butyl]-2,5-dihydro-pyrrole-1-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  Cleavage of a chiral auxiliary using RCM on an especially sterically crowded alkene: Syntheses of chiral carbo- and heterocycles

  摘要：

  Chiral 1,5-, 1,6-, and 1,7-dienes generated in 3-4 steps from chiral auxiliary p-menthane-3-carboxaldehyde undergo RCM with notable discrepancies in reactivity depending on the nature and number of substituents flanking the central double bond. The chiral auxiliary is thus cleaved releasing a carbo- or heterocycle in the process. Special features concerning the RCM on these especially crowded systems are discussed. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2006.07.028

文献信息

• Sterically Biased 3,3-Sigmatropic Rearrangement of Chiral Allylic Azides: Application to the Total Syntheses of Alkaloids
  作者：Sophie Lauzon、François Tremblay、David Gagnon、Cédrickx Godbout、Christine Chabot、Catherine Mercier-Shanks、Stéphane Perreault、Hélène DeSève、Claude Spino

  DOI：10.1021/jo800817p

  日期：2008.8.1

  We describe a tandem Mitsunobu/3,3-sigmatropic rearrangement of allylic azides on a chiral auxiliary system that favors one regioisomer thanks to its exceptional steric bias. The sequence may be completed by the oxidative cleavage of the auxiliary or by a ring-closing metathesis reaction that produces a carboor heterocycle directly and a recyclable form of the chiral auxiliary. Applications of the methodology to the total synthesis of (+)-coniine, (+)-lentiginosin, and (+)-pumiliotoxin C are reported.
• Cleavage of a chiral auxiliary using RCM on an especially sterically crowded alkene: Syntheses of chiral carbo- and heterocycles
  作者：Claude Spino、Luc Boisvert、Jasmin Douville、Stéphanie Roy、Sophie Lauzon、Joannie Minville、David Gagnon、Francis Beaumier、Christine Chabot

  DOI：10.1016/j.jorganchem.2006.07.028

  日期：2006.12

  Chiral 1,5-, 1,6-, and 1,7-dienes generated in 3-4 steps from chiral auxiliary p-menthane-3-carboxaldehyde undergo RCM with notable discrepancies in reactivity depending on the nature and number of substituents flanking the central double bond. The chiral auxiliary is thus cleaved releasing a carbo- or heterocycle in the process. Special features concerning the RCM on these especially crowded systems are discussed. (c) 2006 Elsevier B.V. All rights reserved.