(R)-(-)-(2,2-Diphenylcyclopentoxy)ethene | 163982-20-5

• 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: (R)-(-)-(2,2-Diphenylcyclopentoxy)ethene
• 英文别名: (R)-2,2-diphenyl-1-ethenoxycyclopentane；(R)-2,2-diphenylcyclopentoxyethene；[(2R)-2-ethenoxy-1-phenylcyclopentyl]benzene
• CAS: 163982-20-5
• 化学式: C₁₉H₂₀O
• 分子量: 264.367
• InChiKey: WWMCIICATGOPMD-GOSISDBHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (R)-(-)-(2,2-Diphenylcyclopentoxy)ethene 以89%的产率得到
  参考文献：
  名称：

  Denmark Scott E., Marcin Lawrence R., J. Org. Chem, 60 (1995) N 10, S 3221-3235

  摘要：

  DOI：
• 作为产物：
  描述：

  乙烯基正丁醚 、 (R)-(-)-2,2-diphenylcyclopentanol 在 mercury(II) diacetate 作用下， 反应 24.0h， 以70%的产率得到(R)-(-)-(2,2-Diphenylcyclopentoxy)ethene
  参考文献：
  名称：

  Nitroalkene Inter [4 + 2]/Intra [3 + 2] Tandem Cycloadditions. 7. Application of (R)-(-)-2,2-Diphenylcyclopentanol as the Chiral Auxiliary

  摘要：

  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.

  DOI：

  10.1021/jo00115a042

文献信息

• Tandem [4 + 2]/[3 + 2] Cycloadditions of Nitroalkenes. 9. Synthesis of (−)-Rosmarinecine
  作者：Scott E. Denmark、Atli Thorarensen、Donald S. Middleton

  DOI：10.1021/ja961630x

  日期：1996.1.1

  general approach for the construction of pyrrolizidines having this stereochemical feature. The key step in the asymmetric synthesis is a Lewis acid-promoted, tandem inter-[4 + 2]/intra-[3 + 2] cycloaddition between a fumaroyloxy nitroalkene and a chiral vinyl ether.

  (-)-Rosmarinecine (2) 是吡咯里西啶生物碱 (-)-rosmarinine 的 necine 碱基部分。(-)-Rosmarinecine 是一组吡咯里西啶的代表，除了高度氧化的骨架外，相邻立体中心 C(1)、C(7) 和 C(7a) 之间显示顺式关系。(-)-迷迭香碱 (2) 分八步合成，总产率为 14.8%，作为构建具有这种立体化学特征的吡咯里西啶的一般方法的说明。不对称合成中的关键步骤是富马酰氧基硝基烯烃和手性乙烯基醚之间的路易斯酸促进的串联 [4 + 2] 间/[3 + 2] 内环加成。
• Asymmetric Construction of a Quaternary Carbon Center by Tandem [4 + 2]/[3 + 2] Cycloaddition of a Nitroalkene. The Total Synthesis of (−)-Mesembrine
  作者：Scott E. Denmark、Lawrence R. Marcin

  DOI：10.1021/jo970079z

  日期：1997.3.1

  An efficient, total synthesis of the Sceletium alkaloid (-)-mesembrine is accomplished in seven steps and 19% yield from a functionalized nitroalkene (itself prepared in six steps and 34% yield from ethyl 3-bromopropionate). The construction of the octahydroindole framework of mesembrine features a tandem inter [4 + 2]/intra [3 + 2] cycloaddition of a 2,2-disubstituted 1-nitroalkene and a chiral vinyl ether derived from (1R,2S)-2-(l-methyl-l-phenylethyl)cyclo as the central strategic element. The two stereogenic centers of the natural product, which include a benzylic, quaternary center, were established in 26/1 selectivity in the tandem process.
• Asymmetric Nitroalkene [4 + 2] Cycloadditions: Enantioselective Synthesis of 3-Substituted and 3,4-Disubstituted Pyrrolidines
  作者：Scott E. Denmark、Lawrence R. Marcin

  DOI：10.1021/jo00115a043

  日期：1995.5

  2-Substituted 1-nitroalkenes undergo highly diastereoselective, Lewis-acid-promoted, [4 + 2] cycloaddition with chiral vinyl ethers derived from (R)-2,2-diphenylcyclopentanol and (1R,2S)-2-phenylcyclohexanol to afford cyclic nitronates in high yields. The resulting nitronates were reduced with hydrogen at 160 psi in the presence of platinum oxide to afford enantiomerically enriched pyrrolidines (both as the free base and N-protected derivatives) in good yields. A series of 3-substituted pyrrolidines (71-97% ee) were prepared, as well as (3S,4R)-4-methyl-3-phenyl-N-(p-tolylsulfonyl)pyrrolidine (92% ee) and (3S,4S)-3,4-diphenylpyrrolidine (99% ee). The chiral auxiliaries can be recovered in nearly quantitative yields after hydrogenation.
• (R)-(−)-2,2-DIPHENYLCYCLOPENTANOL
  作者：Denmark, Scott E.、Marcin, Lawrence R.、Schnute, Mark E.、Thorarensen, Atli

  DOI：10.15227/orgsyn.074.0033

  日期：——
• A General Strategy for the Synthesis of Cis-Substituted Pyrrolizidine Bases. The Synthesis of (-)-Rosmarinecine
  作者：Scott E. Denmark、Atli Thorarensen、Donald S. Middleton

  DOI：10.1021/jo00117a002

  日期：1995.6