2-iodo-3,3-dimethylbutanoyl chloride | 1035948-79-8

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 酰卤
• 英文名称: 2-iodo-3,3-dimethylbutanoyl chloride
• CAS: 1035948-79-8
• 化学式: C₆H₁₀ClIO
• 分子量: 260.502
• InChiKey: NNSVGGLNDKXYMW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  9.0
• 可旋转键数：
  1.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  N-(tert-butyl)but-3-en-1-amine 、 2-iodo-3,3-dimethylbutanoyl chloride 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以76%的产率得到N-(but-3-enyl)-N-tert-butyl-2-iodo-3,3-dimethylbutanamide
  参考文献：
  名称：

  α-氨基甲酰基自由基的6 - Exo环化的立体选择性

  摘要：

  实验和理论上研究了α-氨基甲酰基自由基在6 - exo环化中的立体选择性。进行了由BEt 3 / O 2引发的取代的N-（but-3-en-1-yl）-N-（叔丁基）-2-碘代烷酰胺的碘原子转移自由基环化反应，导致3,4-顺式，4,5-反式或4,6-反式取代的δ-内酰胺的主要形成。在B3LYP / 6-31G *级别的密度泛函计算表明，6- exo自由基环化通过船构构过渡态进行。此外，提供了对立体选择性的机械见解，计算结果与实验观察结果非常吻合。

  DOI：

  10.1021/acs.joc.6b00008

文献信息

• Efficient Regio- and Stereoselective Formation of Azocan-2-ones via 8-<i>Endo</i> Cyclization of α-Carbamoyl Radicals
  作者：Xinqiang Fang、Kun Liu、Chaozhong Li

  DOI：10.1021/ja9082649

  日期：2010.2.24

  The iodine-atom-transfer 8-endo cyclization of alpha-carbamoyl radicals was investigated experimentally and theoretically. With the aid of Mg(ClO4)(2) and a bis(oxazoline) ligand, N-ethoxycarbonyl-substituted N-(pent-4-enyl)-2-iodoalkanamides underwent 8-endo cyclization leading to the formation of only the corresponding 3,5-trans-substituted azocan-2-ones in excellent yields Similarly, the BF3 center dot OEt2/H2O-promoted reactions of N-ethoxycarbonyl-N-(2-allylaryl)-2-iodoalkanamides afforded exclusively the benzazocanone products with a 3,5-cis configuration in high yields The bidentate chelation of substrate radicals not only significantly improved the efficiency of cyclization but also resulted in the change of stereochemistry of azocanone products from 3,8-trans to 3,8-cis Theoretical calculations at the UB3LYP/6-31G* level revealed that the cyclization of N-carbonyl-substituted alpha-carbamoyl radicals occurs via the E-conformational transition states without the presence of a Lewis acid. On the other hand, the cyclization proceeds via the Z-conformational transition states when the substrates form the bidentate chelation with a Lewis acid In both cases, the 8-endocyclization is always fundamentally preferred over the corresponding 7-exo cyclization The complexed radicals having the more rigid conformations also allow the better stereochemical control in the iodine-atom-abstraction step To further understand the reactivity of alpha-carbamoyl radicals, the competition between the 8-endo and 5-exo cyclization was also studied The results demonstrated that the 8-endo cyclization is of comparable rate to the corresponding 5-exo cyclization for alpha-carbamoyl radicals with fixed Z-conformational transition states As a comparison, the 8-endo mode is fundamentally preferred over the 5-exo mode in the cyclization of INIH-amide substrates because the latter requires the Z-conformational transition states, whereas the former proceeds via the more stable E-conformational transition states.