N-Benzyl-N-{(S)-1-[(1R,2S)-2-(tert-butyl-diphenyl-silanyloxymethyl)-2-phenyl-cyclopropyl]-ethyl}-hydroxylamine | 810675-87-7

• 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: N-Benzyl-N-{(S)-1-[(1R,2S)-2-(tert-butyl-diphenyl-silanyloxymethyl)-2-phenyl-cyclopropyl]-ethyl}-hydroxylamine
• 英文别名: N-benzyl-N-[(1S)-1-[(1R,2S)-2-[[tert-butyl(diphenyl)silyl]oxymethyl]-2-phenylcyclopropyl]ethyl]hydroxylamine
• CAS: 810675-87-7
• 化学式: C₃₅H₄₁NO₂Si
• 分子量: 535.802
• InChiKey: AQTUWILCPFXSSK-HGECIYNYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  39
• 可旋转键数：
  11
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  32.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-Benzyl-N-{(S)-1-[(1R,2S)-2-(tert-butyl-diphenyl-silanyloxymethyl)-2-phenyl-cyclopropyl]-ethyl}-hydroxylamine 在 四丁基氟化铵 、 溶剂黄146 、 锌 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 15.0h， 生成 (1S,2R)-2-[(S)-1-(benzylamino)ethyl]-1-hydroxymethyl-1-phenylcyclopropane
  参考文献：
  名称：

  Highly Stereoselective Grignard Addition to Cis-Substituted C-Cyclopropylaldonitrones. The Bisected s-Trans Transition State Can Be Stabilized Effectively by the Lewis Acid-Coordination

  摘要：

  We previously found that Grignard addition to a C-cyclopropylaldonitrone, C-[cis-2-(N,N-diethyl-carbamoyl)-trans-2-phenylcyclopropyl]-N-benzylaldonitrone (1), stereoselectively gave the antiproduct 3, in which the stereoselectivity was particularly high when MgBr2 was the additive. In this study, the reaction pathway was investigated in detail. The stereoselective addition was initially thought to occur via either a 1,5-chelation-controlled or a bisected s-trans conformation-controlled pathway. However, Grignard addition to a nonchelating silyl ether-type substrate, C-[cis-2-(tert-butyldiphenylsilyloxymethyl)-trans-2-phenylcyclopropyl]-N-benzylaldonitrone (7), also gave the antiproduct 9 with high stereoselectivity suggesting that chelation is not important in the reaction. Theoretical calculations of C-cyclopropylaldonitrones showed that the coordination of Mg2+ at the nitrone oxygen significantly stabilizes the bisected s-trans conformer due to the effective hyper-conjugation between the,pi* of the nitrone C=N bond and the electron-donating cyclopropane orbitals. This kind of orbital interaction is able to stabilize the transition state of the nucleophilic addition and is maximized in the bisected conformation, in which the orbitals of the forming bond and the cyclopropane C-C bond are in an almost planar arrangement. Thus, the high stereoselectivity can be explained by nucleophilic attack on the less hindered side of the C=N bond of the substrates in the Mg2+-coordinated bisected s-trans conformation.

  DOI：

  10.1021/jo048637e
• 作为产物：
  描述：

  N-苄基羟胺盐酸盐 在 magnesium bromide 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 甲苯 为溶剂， 反应 10.0h， 生成 N-Benzyl-N-{(S)-1-[(1R,2S)-2-(tert-butyl-diphenyl-silanyloxymethyl)-2-phenyl-cyclopropyl]-ethyl}-hydroxylamine
  参考文献：
  名称：

  Highly Stereoselective Grignard Addition to Cis-Substituted C-Cyclopropylaldonitrones. The Bisected s-Trans Transition State Can Be Stabilized Effectively by the Lewis Acid-Coordination

  摘要：

  We previously found that Grignard addition to a C-cyclopropylaldonitrone, C-[cis-2-(N,N-diethyl-carbamoyl)-trans-2-phenylcyclopropyl]-N-benzylaldonitrone (1), stereoselectively gave the antiproduct 3, in which the stereoselectivity was particularly high when MgBr2 was the additive. In this study, the reaction pathway was investigated in detail. The stereoselective addition was initially thought to occur via either a 1,5-chelation-controlled or a bisected s-trans conformation-controlled pathway. However, Grignard addition to a nonchelating silyl ether-type substrate, C-[cis-2-(tert-butyldiphenylsilyloxymethyl)-trans-2-phenylcyclopropyl]-N-benzylaldonitrone (7), also gave the antiproduct 9 with high stereoselectivity suggesting that chelation is not important in the reaction. Theoretical calculations of C-cyclopropylaldonitrones showed that the coordination of Mg2+ at the nitrone oxygen significantly stabilizes the bisected s-trans conformer due to the effective hyper-conjugation between the,pi* of the nitrone C=N bond and the electron-donating cyclopropane orbitals. This kind of orbital interaction is able to stabilize the transition state of the nucleophilic addition and is maximized in the bisected conformation, in which the orbitals of the forming bond and the cyclopropane C-C bond are in an almost planar arrangement. Thus, the high stereoselectivity can be explained by nucleophilic attack on the less hindered side of the C=N bond of the substrates in the Mg2+-coordinated bisected s-trans conformation.

  DOI：

  10.1021/jo048637e

文献信息

• Highly Stereoselective Grignard Addition to <i>Cis</i>-Substituted <i>C</i>-Cyclopropylaldonitrones. The Bisected <i>s</i>-<i>Trans</i> Transition State Can Be Stabilized Effectively by the Lewis Acid-Coordination
  作者：Yuji Kazuta、Hiroshi Abe、Akira Matsuda、Satoshi Shuto

  DOI：10.1021/jo048637e

  日期：2004.12.1

  We previously found that Grignard addition to a C-cyclopropylaldonitrone, C-[cis-2-(N,N-diethyl-carbamoyl)-trans-2-phenylcyclopropyl]-N-benzylaldonitrone (1), stereoselectively gave the antiproduct 3, in which the stereoselectivity was particularly high when MgBr2 was the additive. In this study, the reaction pathway was investigated in detail. The stereoselective addition was initially thought to occur via either a 1,5-chelation-controlled or a bisected s-trans conformation-controlled pathway. However, Grignard addition to a nonchelating silyl ether-type substrate, C-[cis-2-(tert-butyldiphenylsilyloxymethyl)-trans-2-phenylcyclopropyl]-N-benzylaldonitrone (7), also gave the antiproduct 9 with high stereoselectivity suggesting that chelation is not important in the reaction. Theoretical calculations of C-cyclopropylaldonitrones showed that the coordination of Mg2+ at the nitrone oxygen significantly stabilizes the bisected s-trans conformer due to the effective hyper-conjugation between the,pi* of the nitrone C=N bond and the electron-donating cyclopropane orbitals. This kind of orbital interaction is able to stabilize the transition state of the nucleophilic addition and is maximized in the bisected conformation, in which the orbitals of the forming bond and the cyclopropane C-C bond are in an almost planar arrangement. Thus, the high stereoselectivity can be explained by nucleophilic attack on the less hindered side of the C=N bond of the substrates in the Mg2+-coordinated bisected s-trans conformation.