(1R,3S,5aR,7aR,7bS)-Octahydro-1-hydroxy-7b-methyl-2H-cyclopentapyrrolizin-2-one | 137624-81-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯里西啶类
• 英文名称: (1R,3S,5aR,7aR,7bS)-Octahydro-1-hydroxy-7b-methyl-2H-cyclopentapyrrolizin-2-one
• 英文别名: (3R,4R,7R,10S)-3-hydroxy-10-methyl-1-azatricyclo[5.2.1.04,10]decan-2-one
• CAS: 137624-81-8
• 化学式: C₁₀H₁₅NO₂
• 分子量: 181.235
• InChiKey: LXULSPLKUUHRCA-JIOCBJNQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  40.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3,5-dinitrobenzoyl azide 、 (1R,3S,5aR,7aR,7bS)-Octahydro-1-hydroxy-7b-methyl-2H-cyclopentapyrrolizin-2-one 以 甲苯 为溶剂， 反应 1.0h， 以76%的产率得到(1R,3S,5aR,7aR,7bS)-octahydro-1--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：

  (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

文献信息

• Nitroalkene Inter [4 + 2]/Intra [3 + 2] Tandem Cycloadditions. 7. Application of (R)-(-)-2,2-Diphenylcyclopentanol as the Chiral Auxiliary
  作者：Scott E. Denmark、Mark E. Schnute、Lawrence R. Marcin、Atli Thorarensen

  DOI：10.1021/jo00115a042

  日期：1995.5

  Chiral enol ethers derived from (R)-(-)-2,2-diphenylcyclopentanol ((-)-3) have been found to provide high levels of asymmetric induction in tandem inter [4 + 2]/intra [3 + 2] nitroalkene cycloadditions. The chiral auxiliary (>97% ee) is readily prepared in three steps from diphenylacetonitrile employing an asymmetric oxazaborolidine-catalyzed borane reduction. Either enantiomeric series of tandem cycloaddition/hydrogenolysis product 7 is available from the chiral auxiliary of a single absolute configuration by judicious selection of the Lewis acid promoter, Ti(O-i-Pr)(2)Cl-2 (98% ee, (-)-7) or MAPh (93% ee, (+)-7). Propenyl ethers derived from (-)-3 undergo endo selective [4 + 2] cycloadditions (2.3/1 - 8.2/1) in the presence Ti(O-i-Pr)(2)Cl-2; however, exo selective [4 + 2] cycloadditions (10.2/1 - 54.8/1) are observed in the presence of MAPh.
• DENMARK, SCOTT E.;MOON, YOUNG-CHOON;SENANAYAKE, C. B. W., J. AMER. CHEM. SOC., 112,(1990) N, C. 311-315
  作者：DENMARK, SCOTT E.、MOON, YOUNG-CHOON、SENANAYAKE, C. B. W.

  DOI：——

  日期：——
• 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.