triisopropylsilyl propylideneazinate | 1181217-66-2

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: triisopropylsilyl propylideneazinate
• 英文别名: N-tri(propan-2-yl)silyloxypropan-1-imine oxide
• CAS: 1181217-66-2
• 化学式: C₁₂H₂₇NO₂Si
• 分子量: 245.437
• InChiKey: USFQZOBCXBNCPZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.08
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  38
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  triisopropylsilyl propylideneazinate 在 sodium tetrahydroborate 、 copper(II) bis(trifluoromethanesulfonate) 、 S-4,5-二氢-2-(2-((S)-4,5-二氢-4-异丙基噁唑-2-基)丙-2-基)-4-异丙基噁唑 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 [(3S,4R,5R)-3-ethyl-4-methoxycarbonyl-N-triisopropylsilyloxy-2-isoxazolidin-5-yl]methanol
  参考文献：
  名称：

  Silyl Nitronate Cycloadditions Catalyzed by Cu(II)-Bisoxazoline

  摘要：

  Cu(OTf)(2) and chiral BOX ligand-catalyzed 1,3-dipolar cydoadditions Of triisopropylsilyl nitronates with alpha,beta-unsaturated carboximides produced chiral isoxazolines in high yields, high enantioselectivities, and complete diastereoselectivities. These chiral isoxazoline products were further converted into structurally diversified derivatives, which demonstrated the utility of the new method of constructing isoxazolines. The transition-state structure of cydoaddition was proposed in the light of the relative and absolute configurations of the products.

  DOI：

  10.1021/acs.joc.5b02035
• 作为产物：
  描述：

  三异丙基氯硅烷 、 硝基丙烷 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 以79%的产率得到triisopropylsilyl propylideneazinate
  参考文献：
  名称：

  Enantioselective Aldehyde α-Nitroalkylation via Oxidative Organocatalysis

  摘要：

  The first enantioselective organocatalytic alpha-nitroatkylation of aldehydes has been accomplished. The aforementioned process involves the oxidative coupling of an enamine intermediate, generated transiently via condensation of an amine catalyst with an aldehyde, with a silyl. nitronate to produce a beta-nitroaldehyde. Two methods, one that furnishes the syn beta-nitroaldehyde and a second that provides access to the anti isomer, have been developed. Data are presented to support a hypothesis that explains this phenomenon in terms of a silyl group-controlled change in mechanism. Finally, a three-step procedure for the synthesis of both syn- and anti-alpha,beta-disubstituted beta-amino acids is presented.

  DOI：

  10.1021/ja904504j

文献信息

• Tandem [3+2]-cycloaddition/homo-Baldwin rearrangement of silyl nitronates and donor-acceptor cyclopropenes. A novel approach to polysubstituted aziridines starting from nitro compounds
  作者：Yana I. Lichtenstein、Ivan S. Golovanov、Sema L. Ioffe、Andrey A. Tabolin

  DOI：10.1016/j.tet.2022.132693

  日期：2022.3

  The synthesis of substituted N-silyloxy aziridines through reaction of silyl nitronates and enol diazo acetates is described. The process involves in situ transformation of enol diazo acetates into donor-acceptor cyclopropenes, their [3 + 2]-cycloaddition with nitronates and subsequent rearrangement of fused isoxazolidine intermediates. Depending on the substrate type, generation of prerequisite cyclopropenes

  描述了通过硝酸甲硅烷基酯和烯醇重氮乙酸酯反应合成取代的N-甲硅烷氧基氮丙啶。该过程包括将烯醇重氮乙酸酯原位转化为供体-受体环丙烯，它们与硝酸盐的[3 + 2]-环加成以及随后稠合的异恶唑烷中间体的重排。根据底物类型，在催化剂负载量低至 50 ppm 的情况下，各种羧酸铑（乙酸盐、辛酸盐）可以促进必要环丙烯的生成。氮丙啶环中所有三个立体中心的相对构型由 NMR 技术确定，并得到量子化学计算的支持。