(S)-ethyl 2-[(R)-cyclohexanesulfinamido]-3,3-dimethylbutanoate | 1465119-79-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (S)-ethyl 2-[(R)-cyclohexanesulfinamido]-3,3-dimethylbutanoate
• 英文别名: ethyl (2S)-2-[[(R)-cyclohexylsulfinyl]amino]-3,3-dimethylbutanoate
• CAS: 1465119-79-2
• 化学式: C₁₄H₂₇NO₃S
• 分子量: 289.439
• InChiKey: LIDDHUAOZAMOKC-CWTRNNRKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  74.6
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  碘环己烷 在 1,2-二溴乙烷 、 nickel(II) acetylacetonate 作用下， 以 四氢呋喃 为溶剂， 反应 22.33h， 生成 (S)-ethyl 2-[(S)-cyclohexanesulfinamido]-3,3-dimethylbutanoate 、 (S)-ethyl 2-[(R)-cyclohexanesulfinamido]-3,3-dimethylbutanoate
  参考文献：
  名称：

  Radical Migration–Addition of N-tert-Butanesulfinyl Imines with Organozinc Reagents

  摘要：

  A novel migration-addition sequence was discovered for the reaction of enantioenriched N-tert-butanesulfinyl with iminoacetate la functionalized benzylzinc bromide reagents, producing tert-leucine derivatives in excellent diastereoselectivity (dr 98:2). The absolute configurations of two new chiral centers were unambiguously assigned by chemical transformations and X-ray crystallography. In addition, the regio- and diastereoselectivities of this novel reaction were both explained through the key N-sulfinamine intermediate M6 generated by the tert-butyl radical attack on the imine. Computational analysis of this reaction process, which was performed at the B3LYP/6-311++G(3df,2p)//B3LYP/6-31G*-LANL2DZ level, also supported our proposed two-stage mechanism.

  DOI：

  10.1021/jo401640c

文献信息

• Radical Migration–Addition of <i>N</i>-<i>tert-</i>Butanesulfinyl Imines with Organozinc Reagents
  作者：Wei Huang、Jian-Liang Ye、Wei Zheng、Han-Qing Dong、Bang-Guo Wei

  DOI：10.1021/jo401640c

  日期：2013.11.15

  A novel migration-addition sequence was discovered for the reaction of enantioenriched N-tert-butanesulfinyl with iminoacetate la functionalized benzylzinc bromide reagents, producing tert-leucine derivatives in excellent diastereoselectivity (dr 98:2). The absolute configurations of two new chiral centers were unambiguously assigned by chemical transformations and X-ray crystallography. In addition, the regio- and diastereoselectivities of this novel reaction were both explained through the key N-sulfinamine intermediate M6 generated by the tert-butyl radical attack on the imine. Computational analysis of this reaction process, which was performed at the B3LYP/6-311++G(3df,2p)//B3LYP/6-31G*-LANL2DZ level, also supported our proposed two-stage mechanism.