t-butyldiphenylsilyl propylideneazinate | 1181217-68-4

• 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: t-butyldiphenylsilyl propylideneazinate
• 英文别名: t-butyldiphenylsilylpropylideneazinate
• CAS: 1181217-68-4
• 化学式: C₁₉H₂₅NO₂Si
• 分子量: 327.499
• InChiKey: RBFSRAWROWZZOM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.47
• 重原子数：
  23.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  35.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  t-butyldiphenylsilyl propylideneazinate 、 正己醛 在 ammonium cerium (IV) nitrate 、 5-benzyl-2-t-butyl-3-methyl-4-oxoimidazolidinium trifluoroacetate 、 水 、 sodium 2,2,2-trifluoroacetate 作用下， 以 丙酮 为溶剂， 反应 16.0h， 生成 2-[1-nitropropyl]hexanal 、 2-[1-nitropropyl]hexanal
  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
• 作为产物：
  描述：

  硝基丙烷 、 叔丁基二苯基氯硅烷 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， 生成 t-butyldiphenylsilyl 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。