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 | 124126-12-1

• 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: 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
• 英文别名: rel-(1S,5aS,7aS,7bR)-octahydro-1-hydroxy-7b-methyl-2H-cyclopenta[gh]pyrrolizin-2-one；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；(3S,4S,7S,10R)-3-hydroxy-10-methyl-1-azatricyclo[5.2.1.04,10]decan-2-one
• CAS: 124126-12-1；130857-42-0；137624-81-8；147253-74-5
• 化学式: C₁₀H₁₅NO₂
• 分子量: 181.235
• InChiKey: LXULSPLKUUHRCA-PYHGXSLLSA-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：

  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 在 硼烷四氢呋喃络合物 、 cerium(III) chloride heptahydrate 、 三氧化硫吡啶 、 sodium hydride 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 二甲基亚砜 、 N,N-二甲基甲酰胺 为溶剂， 反应 6.58h， 生成 (1S,3S,5aS,7aS,7bR)-octahydro-1-benzyloxy-1-isopropyl-7b-methyl-2H-cyclopenta[gh]pyrrolizine*3-borane
  参考文献：
  名称：

  A Systematic Investigation of Quaternary Ammonium Ions as Asymmetric Phase-Transfer Catalysts. Synthesis of Catalyst Libraries and Evaluation of Catalyst Activity

  摘要：

  Despite over three decades of research into asymmetric phase-transfer catalysis (APTC), a fundamental understanding of the factors that affect the rate and stereoselectivity of this important process are still obscure. This paper describes the initial stages of a long-term program aimed at elucidating the physical organic foundations of APTC employing a chemoinformatic analysis of the alkylation of a protected glycine imine with libraries of enantiomerically enriched quaternary ammonium ions. The synthesis of the quaternary ammonium ions follows a diversity:oriented approach wherein the tandem inter [4 + 2]/intra[3 + 2] cycloaddition of nitroalkenes serves as the key transformation. A two-part synthetic strategy comprised of (1) preparation of enantioenriched scaffolds and (2) development of parallel synthesis procedures is described. The strategy allows for the facile introduction of four variable groups in the vicinity of a stereogenic quaternary ammonium ion. The quaternary ammonium ions exhibited a wide range of activity and to a lesser degree enantioselectivity. Catalyst activity and selectivity are rationalized in a qualitative way on the basis of the effective positive potential of the ammonium ion.

  DOI：

  10.1021/jo2005445
• 作为产物：
  描述：

  methyl rel-(1R,3S,5R,6aR,8aR,8bS)-5-butoxy-8b-methyl-6a,7,8,8a-tetrahydrocyclopenta<1,2,3-hj>isooxazolo<2,3-b><1,2>oxazine-1-carboxylate 在 镍 氢气 作用下， 以 甲醇 为溶剂， 反应 24.0h， 以81%的产率得到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
  参考文献：
  名称：

  串联 [4 + 2]/[3 + 2] 环加成：多环框架的简单立体选择性构建

  摘要：

  我们在此描述了一个简单的策略，它通过将 1,3-偶极环加成与产生它们的 [4+2] 过程进行分子内偶联来扩展硝基的效用

  DOI：

  10.1021/ja00157a048

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。
• Studies on the reduction and hydrolysis of nitroso acetals
  作者：Scott E Denmark、Vito Guagnano、Jean Vaugeois

  DOI：10.1139/v01-132

  日期：2001.11.1

  Chemical transformation of nitroso acetals derived from tandem [4 + 2]/[3 + 2] cycloadditions of nitroalkenes have been investigated. New reduction methods were surveyed in an attempt to supplant the use of hydrogen and Raney nickel. Homogeneous catalytic hydrogenation was not successful, but samarium diiodide did effectively and selectively cleave one of the N—O bonds in a number of nitroso acetals. Acid-promoted hydrolysis of the nitroso acetals produced both α-alkoxy nitrones and hydroxamic acids selectively via expected pathways.Key words: nitroso acetals, hydroxamic acids, α-alkoxy nitrones, reduction, hydrolysis.

  研究了从串联[4+2]/[3+2]环加成的硝基烯烃中得到的硝酰缩醛的化学转化。尝试调查了新的还原方法，以取代氢和Raney镍的使用。均相催化氢化不成功，但是二碘化钐在多种硝酰缩醛中有效地选择性地裂解了其中一个N-O键。酸促进的硝酰缩醛水解通过预期的途径产生了α-烷氧基亚硝基酮和羟肟酸。关键词：硝酰缩醛、羟肟酸、α-烷氧基亚硝基酮、还原、水解。
• 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 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.
• 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.