ethyl 2-allylphenyl(2-iodo-3,3-dimethylbutanoyl)carbamate | 1211566-09-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: ethyl 2-allylphenyl(2-iodo-3,3-dimethylbutanoyl)carbamate
• CAS: 1211566-09-4
• 化学式: C₁₈H₂₄INO₃
• 分子量: 429.298
• InChiKey: GFTQZWHKMPTTBP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.75
• 重原子数：
  23.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  46.61
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  ethyl 2-allylphenyl(2-iodo-3,3-dimethylbutanoyl)carbamate 在 三乙基硼 、 三氟化硼乙醚 、 水 、 氧气 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以73%的产率得到(3,5-cis)-ethyl 3-tert-butyl-5-iodo-2-oxo-3,4,5,6-tetrahydrobenzo[b]azocine-1(2H)-carboxylate
  参考文献：
  名称：

  Efficient Regio- and Stereoselective Formation of Azocan-2-ones via 8-Endo Cyclization of α-Carbamoyl Radicals

  摘要：

  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.

  DOI：

  10.1021/ja9082649
• 作为产物：
  描述：

  2-iodo-3,3-dimethylbutanoyl chloride 、 N-Ethoxycarbonyl-2-allyl-anilin 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.5h， 生成 ethyl 2-allylphenyl(2-iodo-3,3-dimethylbutanoyl)carbamate
  参考文献：
  名称：

  Efficient Regio- and Stereoselective Formation of Azocan-2-ones via 8-Endo Cyclization of α-Carbamoyl Radicals

  摘要：

  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.

  DOI：

  10.1021/ja9082649