(2S,2aR,4aR,6R,7aR,7bS)-6-<(1R,2S)-2-(phenylcyclohexyl)oxy>octahydro-7b-methyl-1,7-dioxa-7a-azacyclopentindene-2-carboxylic acid methyl ester | 137624-84-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 恶嗪烷类
• 英文名称: (2S,2aR,4aR,6R,7aR,7bS)-6-<(1R,2S)-2-(phenylcyclohexyl)oxy>octahydro-7b-methyl-1,7-dioxa-7a-azacyclopentindene-2-carboxylic acid methyl ester
• 英文别名: methyl (3R,4R,7R,9S,11S)-11-methyl-9-[(1R,2S)-2-phenylcyclohexyl]oxy-2,10-dioxa-1-azatricyclo[5.3.1.04,11]undecane-3-carboxylate
• CAS: 137624-84-1
• 化学式: C₂₃H₃₁NO₅
• 分子量: 401.503
• InChiKey: XGCDSOUVOLRBLD-HBRPHFHUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  29
• 可旋转键数：
  5
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  57.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (2S,2aR,4aR,6R,7aR,7bS)-6-<(1R,2S)-2-(phenylcyclohexyl)oxy>octahydro-7b-methyl-1,7-dioxa-7a-azacyclopentindene-2-carboxylic acid methyl ester 在 镍 氢气 作用下， 以 甲醇 为溶剂， 反应 24.0h， 以76%的产率得到(1R,3S,5aR,7aR,7bS)-Octahydro-1-hydroxy-7b-methyl-2H-cyclopentapyrrolizin-2-one
  参考文献：
  名称：

  Tandem inter [4+2]/intra [3+2]nitroalkene cycloadditions. 5. Origin of the Lewis acid dependent reversal of stereoselectivity

  摘要：

  The stereochemical course of the tandem [4 + 2]/[3 + 2] nitroalkene cycloaddition with chiral enol ethers has been shown to exhibit remarkable sensitivity to the nature of the Lewis acid promoter. Cycloadditions using (+)-camphor-derived vinyl ether 3 or (-)-trans-2-phenylcyclohexanol-derived vinyl ether 6 gave a predominance of the 1S hydroxy lactam 4 when promoted by Ti(O-i-Pr)2Cl2. The same vinyl ethers selectively produced the 1R hydroxy lactam 4 when promoted by MAPh. The (E)- and (Z)-1-propenyl ethers of (-)-trans-2-phenylcyclohexanol have been used to investigate the reversal of selectivity. Cycloadditions promoted by Ti(O-i-Pr)2Cl2 were found to be endo selective (12:1), while MAD and MAPh favored exo approach of the dienophile. High levels of asymmetric induction were observed in the endo mode of the cycloaddition for propenyl ethers (E)-13 and (Z)-13, 97.9% ee and 82.2% ee, respectively, but an erosion of selectivity occurred in the exo mode (72.2% ee) presumably through an s-cis enol ether conformation.

  DOI：

  10.1021/jo00059a044
• 作为产物：
  描述：

  (1R,2S)-trans-2-phenylcyclohexanol 在 2,6-二苯基苯酚 、 mercury(II) diacetate 、 三甲基铝 作用下， 以 二氯甲烷 为溶剂， 反应 25.0h， 生成 (2S,2aR,4aR,6R,7aR,7bS)-6-<(1R,2S)-2-(phenylcyclohexyl)oxy>octahydro-7b-methyl-1,7-dioxa-7a-azacyclopentindene-2-carboxylic acid methyl ester
  参考文献：
  名称：

  Tandem inter [4+2]/intra [3+2]nitroalkene cycloadditions. 5. Origin of the Lewis acid dependent reversal of stereoselectivity

  摘要：

  The stereochemical course of the tandem [4 + 2]/[3 + 2] nitroalkene cycloaddition with chiral enol ethers has been shown to exhibit remarkable sensitivity to the nature of the Lewis acid promoter. Cycloadditions using (+)-camphor-derived vinyl ether 3 or (-)-trans-2-phenylcyclohexanol-derived vinyl ether 6 gave a predominance of the 1S hydroxy lactam 4 when promoted by Ti(O-i-Pr)2Cl2. The same vinyl ethers selectively produced the 1R hydroxy lactam 4 when promoted by MAPh. The (E)- and (Z)-1-propenyl ethers of (-)-trans-2-phenylcyclohexanol have been used to investigate the reversal of selectivity. Cycloadditions promoted by Ti(O-i-Pr)2Cl2 were found to be endo selective (12:1), while MAD and MAPh favored exo approach of the dienophile. High levels of asymmetric induction were observed in the endo mode of the cycloaddition for propenyl ethers (E)-13 and (Z)-13, 97.9% ee and 82.2% ee, respectively, but an erosion of selectivity occurred in the exo mode (72.2% ee) presumably through an s-cis enol ether conformation.

  DOI：

  10.1021/jo00059a044

文献信息

• Tandem inter [4+2]/intra [3+2] cycloadditions. 3. The stereochemical influence of the Lewis acid
  作者：Scott E. Denmark、Mark E. Schnute

  DOI：10.1021/jo00024a005

  日期：1991.11

  trans-2-Phenylcyclohexanol has been employed as a chiral auxiliary in the inter [4 + 2]/intra [3 + 2] tandem cycloaddition of nitroalkenes with chiral vinyl ethers. A novel reversal of selectivity between cycloadditions catalyzed by the Lewis acids Ti(O-i-Pr)2Cl2 and MAPh has been discovered.