(1S,3R,5aS,7aS,7bR)-1--7b-methyl-2-oxo-5a,6,7,7a-tetrahydrocyclopenta<1,2,3-gi>pyrrolidino<1,2-a>pyrrolidine | 137572-08-8

• 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: (1S,3R,5aS,7aS,7bR)-1--7b-methyl-2-oxo-5a,6,7,7a-tetrahydrocyclopenta<1,2,3-gi>pyrrolidino<1,2-a>pyrrolidine
• 英文别名: (1S,3R,5aS,7aS,7bR)-octahydro-1--7b-methyl-2H-cyclopentapyrrolizin-2-one；(1S,3R,5aS,7aS,7bR)-1--7b-methyloctahydro-2H-cyclopentapyrrolizin-2-one；[(3S,4S,7S,10R)-10-methyl-2-oxo-1-azatricyclo[5.2.1.04,10]decan-3-yl] N-(3,5-dinitrophenyl)carbamate
• CAS: 137572-08-8
• 化学式: C₁₇H₁₈N₄O₇
• 分子量: 390.353
• InChiKey: JAOHKPLLZFHAMM-AMDIRCQMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  28
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  150
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  3,5-dinitrobenzoyl azide 、 rel-(1R,3S,5aR,7aR,7bS)-1-hydroxy-7b-methyl-2-oxo-5a,6,7,7a-tetrahydrocyclopenta<1,2,3-gi>pyrrolidino<1,2-a>pyrrolidine 以 甲苯 为溶剂， 反应 0.17h， 以85%的产率得到(1S,3R,5aS,7aS,7bR)-1--7b-methyl-2-oxo-5a,6,7,7a-tetrahydrocyclopenta<1,2,3-gi>pyrrolidino<1,2-a>pyrrolidine
  参考文献：
  名称：

  串联[4 + 2] / [3 + 2]-环加成。2.手性乙烯基醚的不对称诱导

  摘要：

  乙烯基醚可有效引发串联连接到α，β-不饱和酯双极性亲和剂的硝基烯烃的串联[4 + 2] / [3 + 2]-环加成反应。使用手性乙烯基醚6作为亲二烯体，硝基烯烃1和2经历高度选择性的串联环加成。所得到的亚硝基缩醛的氢解裂解产生了> 98％ee的α-羟基内酰胺（-）- 14和（-）- 21，手性助剂的回收率很高。可以看出，非对映异构体的高选择性源于对乙烯基醚的强烈内在偏爱以及助剂中固有的表面偏向。

  DOI：

  10.1016/s0040-4020(01)85599-x

文献信息

• Tandem [4+2]/[3+2]-cycloadditions. 2. Asymmetric induction with a chiral vinyl ether
  作者：Scott E. Denmark、C.B.W. Senanayake、Ho Ginny-Dai

  DOI：10.1016/s0040-4020(01)85599-x

  日期：1990.1

  A tandem [4+2]/[3+2]-cycloaddition of nitroalkenes tethered to α,β-unsaturated ester dipolarophiles can be effectively triggered with a vinyl ether. Using the chiral vinyl ether 6 as the dienophile, nitroalkenes 1 and 2 undergo highly selective tandem cycloaddition. Hydrogenolytic cleavage of the resulting nitroso acetals produce α-hydroxy lactams (-)-14 and (-)-21 in >98% e.e. with excellent recovery

  乙烯基醚可有效引发串联连接到α，β-不饱和酯双极性亲和剂的硝基烯烃的串联[4 + 2] / [3 + 2]-环加成反应。使用手性乙烯基醚6作为亲二烯体，硝基烯烃1和2经历高度选择性的串联环加成。所得到的亚硝基缩醛的氢解裂解产生了> 98％ee的α-羟基内酰胺（-）- 14和（-）- 21，手性助剂的回收率很高。可以看出，非对映异构体的高选择性源于对乙烯基醚的强烈内在偏爱以及助剂中固有的表面偏向。
• 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.
• Tandem [4 + 2]/[3 + 2] Cycloadditions of Nitroalkenes. 10. <i>trans</i>-2-(1-Methyl-1-phenylethyl)cyclohexanol as a New Auxiliary
  作者：Scott E. Denmark、Atli Thorarensen

  DOI：10.1021/jo960912c

  日期：1996.1.1