(1S,2R,3S,4R)-3-(2,2-dimethylpropoxy)-2-(1-propynyloxy)-4,7,7-trimethylbicyclo<2.2.1>heptane | 147166-16-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1S,2R,3S,4R)-3-(2,2-dimethylpropoxy)-2-(1-propynyloxy)-4,7,7-trimethylbicyclo<2.2.1>heptane
• 英文别名: (1R,2S,3R,4S)-2-(2,2-dimethylpropoxy)-1,7,7-trimethyl-3-prop-1-ynoxybicyclo[2.2.1]heptane
• CAS: 147166-16-3
• 化学式: C₁₈H₃₀O₂
• 分子量: 278.435
• InChiKey: JYFJUAZWOVXANK-ADAWSYLGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1S,2R,3S,4R)-3-(2,2-dimethylpropoxy)-2-(1-propynyloxy)-4,7,7-trimethylbicyclo<2.2.1>heptane 在 钯 喹啉 、 二异丙氧基二氯化钛 、 氢气 作用下， 以 甲醇 、 正己烷 、 二氯甲烷 为溶剂， 25.0 ℃ 、101.33 kPa 条件下， 反应 10.0h， 生成 (2S,2aS,4aS,5R,6S,7aR,7bR)-6-<(1S,2R,3S,4R)-3-(2,2-dimethylpropoxy)-4,7,7-trimethylbicyclo<2.2.1>hept-2-oxy>octahydro-5,7b-dimethyl-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
• 作为产物：
  描述：

  三氯乙烯 、 (1R,2S,3R,4S)-2-(2,2-dimethylpropoxy)-1,7,7-trimethylbicyclo<2.2.1>heptan-3-ol 、 碘甲烷 生成 (1S,2R,3S,4R)-3-(2,2-dimethylpropoxy)-2-(1-propynyloxy)-4,7,7-trimethylbicyclo<2.2.1>heptane
  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]nitroalkene cycloadditions. 5. Origin of the Lewis acid dependent reversal of stereoselectivity
  作者：Scott E. Denmark、Mark E. Schnute、C. B. W. Senanayake

  DOI：10.1021/jo00059a044

  日期：1993.3

  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.