(2R,3R)-tert-butyldimethyl-[3-hydroxy-3-methyl-2-(2-nitrobenzenesulfonylamino)]-pent-4-ynoxysilane | 960595-74-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2R,3R)-tert-butyldimethyl-[3-hydroxy-3-methyl-2-(2-nitrobenzenesulfonylamino)]-pent-4-ynoxysilane
• CAS: 960595-74-8
• 化学式: C₁₈H₂₈N₂O₆SSi
• 分子量: 428.582
• InChiKey: NTCIZHFZZNTJSA-SJLPKXTDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.65
• 重原子数：
  28.0
• 可旋转键数：
  8.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  118.77
• 氢给体数：
  2.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  (2R,3R)-tert-butyldimethyl-[3-hydroxy-3-methyl-2-(2-nitrobenzenesulfonylamino)]-pent-4-ynoxysilane 在 18-冠醚-6 、 偶氮二甲酸二异丙酯 、 三苯基膦 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 2.0h， 生成 N-((2S,3R)-1-((tert-butyldimethylsilyl)oxy)-3-cyano-3-methylpent-4-yn-2-yl)-2-nitrobenzenesulfonamide
  参考文献：
  名称：

  Reactions of carbon nucleophiles with 2,2,3-trisubstituted ethynylaziridines

  摘要：

  Carbon nucleophiles were used to open a 2,2,3-trisubstituted ethynylaziridine. A cyanide nucleophile opened the ring at the more substituted carbon, proceeding regioselectively with inversion of configuration. In an attempt to expand upon the scope of the reaction, Normant cuprates were reacted with a 2,2,3-trisubstituted ethynylaziridine. This reaction produced chiral allenes via an anti-S(N)2' pathway. X-ray analysis of a derivative allowed the absolute stereochemistry of the anti-allenes to be assigned as P. Published by Elsevier Ltd.

  DOI：

  10.1016/j.tetasy.2013.08.009
• 作为产物：
  描述：

  邻硝基苯磺酰氯 在 4-二甲氨基吡啶 、 sodium carbonate 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 生成 (2R,3R)-tert-butyldimethyl-[3-hydroxy-3-methyl-2-(2-nitrobenzenesulfonylamino)]-pent-4-ynoxysilane
  参考文献：
  名称：

  Reactions of carbon nucleophiles with 2,2,3-trisubstituted ethynylaziridines

  摘要：

  Carbon nucleophiles were used to open a 2,2,3-trisubstituted ethynylaziridine. A cyanide nucleophile opened the ring at the more substituted carbon, proceeding regioselectively with inversion of configuration. In an attempt to expand upon the scope of the reaction, Normant cuprates were reacted with a 2,2,3-trisubstituted ethynylaziridine. This reaction produced chiral allenes via an anti-S(N)2' pathway. X-ray analysis of a derivative allowed the absolute stereochemistry of the anti-allenes to be assigned as P. Published by Elsevier Ltd.

  DOI：

  10.1016/j.tetasy.2013.08.009

文献信息

• A Regio- and Stereoselective Approach to Quaternary Centers from Chiral Trisubstituted Aziridines
  作者：Erin M. Forbeck、Cory D. Evans、John A. Gilleran、Pixu Li、Madeleine M. Joullié

  DOI：10.1021/ja0758077

  日期：2007.11.1

  formation of these hindered ethers has been investigated using a variety of functionalized aziridines and phenols to determine the scope of the reaction. Other nucleophiles, such as thiolate, azide, and chloride, have also been examined to encompass the synthesis of a broader range of functionalities. This aziridine ring opening reaction manifold has demonstrated utility in assembling: beta-substituted-alpha-amino

  对区域和立体特异性氮丙啶开环反应的彻底调查提出了用于构建各种季 β-取代-α-氨基官能团的新合成技术。温和、无金属的反应条件允许在高度功能化的系统中应用。该反应已应用于具有挑战性的叔烷基芳基醚的立体选择性形成。已经使用各种官能化氮丙啶和酚类研究了这些受阻醚的形成策略，以确定反应的范围。其他亲核试剂，如硫醇盐、叠氮化物和氯化物，也已被研究以涵盖更广泛的功能的合成。该氮丙啶开环反应歧管已证明可用于组装：β-取代-α-氨基甲酰胺、β-取代-α-氨基酯、β-取代-α-氨基甲硅烷基醚、β-硫代-α-氨基甲酰胺、β-叠氮基-α-氨基甲酰胺和β-卤代-α-氨基甲酰胺。探究氮丙啶取代模式影响的研究表明，烷基氮丙啶显示出与炔基氮丙啶相似的反应性，从而深入了解机理可能性。
• Possible Reason for the Unusual Regioselectivity in Nucleophilic Ring Opening of Trisubstituted Aziridines under Mildly Basic Conditions
  作者：Brandon T. Kelley、Patrick Carroll、Madeleine M. Joullié

  DOI：10.1021/jo5006685

  日期：2014.6.6

  3-Trisubstituted aziridines are known to undergo ring opening at the more substituted carbon under mildly basic conditions. However, the reason for the formation of the more sterically encumbered product has never been examined. Several trisubstituted aziridines, with different substitution patterns at the C-2 and C-3 carbons, were synthesized to change the electronics of the aziridine ring system. These

  已知2,2,3-三取代的氮丙啶在温和的碱性条件下在取代度更高的碳上发生开环。但是，从来没有研究过形成空间上较多的产物的原因。合成了在C-2和C-3碳原子上具有不同取代方式的几种三取代的氮丙啶，以改变氮丙啶环系统的电子学。这些变化对开环反应的区域选择性没有影响。使用B3LYP / 6-31G * DFT基组，确定了在取代度更高的碳处的开环转变态以比取代度更低的碳处的转变态更低的能量进行。