2-[Methoxy(diphenyl)methyl]cyclopent-2-en-1-ol | 218788-51-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: 2-[Methoxy(diphenyl)methyl]cyclopent-2-en-1-ol
• CAS: 218788-51-3
• 化学式: C₁₉H₂₀O₂
• 分子量: 280.367
• InChiKey: GWIHEHSJHRHQRU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  21
• 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：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-[Methoxy(diphenyl)methyl]cyclopent-2-en-1-ol 在 pyridium chlorochromate 作用下， 以56%的产率得到
  参考文献：
  名称：

  Photochemical Generation and Methanol Trapping of Localized 1,3 and 1,4 Singlet Diradicals Derived from a Spiroepoxy-Substituted Cyclopentane-1,3-diyl

  摘要：

  The direct and benzophenone-sensitized photodenitrogenation of the azoalkane 2,3-diazabicyclo-[2.2.1]hept-2-ene-7,3'-spiro-2',2'-diphenyloxirane 1 at ambient temperature (ca. 15 OC) in benzene afforded exclusively the 6-oxabicyclo[3.2.0]hept-1-ene 3. The labile oxetane 3 is proposed to be formed by the selective cleavage of the C-O bond in the epoxy ring of the initially photogenerated, spiroepoxy-substituted, localized cyclopentane-1,3-diyl diradical 1,3-DR to the 1,4-DR diradical and subsequent cyclization of the latter. Even at -100 degrees C, the highly strained (strain energy estimated to be ca. 94 kcal/mol) spiroepoxy housane 2 could not be observed by H-1 NMR (600 MHz) spectroscopy. In MeOH, instead of the oxetane 3, the two regioisomeric MeOH adducts 6 (trapping product of the diradicals 1,3-DR and 1,4-DR) and 6' (methanolysis product of 3) were obtained in high yields. For the first time methanol trapping of a cyclopentane-1,3-diyl singlet diradical was achieved; the required dipolar character is presumably induced in this symmetric species by the polar methanol medium. Computational work (UB3LYP/6-31G*) reveals that the S-1,3-DR singlet diradical possesses a singlet ground state (Delta E-ST ca. 1 kcal/mol), for which ring closure (E-A ca. 2.6 kcal/mol) to the spiroepoxy housane 2 requires more activation than epoxide-ring opening (E-A Ca. 0.7 kcal/mol); the T-1,3-DR triplet species ring-opens spontaneously (E-A Ca. 0 kcal/mol) to the corresponding T-1,4-DR. Stereoelectronic effects dictate the appropriate conformational alignment of the C-O bond with the radical p orbital in the 1,3-DR for the selective cleavage of the C-O rather than C-C bond in the epoxy ring.

  DOI：

  10.1021/ja9822761
• 作为产物：
  描述：

  diethyl 7-(diphenylmethylene)-2,3-diazabicyclo[2.2.1]heptane-2,3-dicarboxylate 在 氢氧化钾 、 间氯过氧苯甲酸 、 copper dichloride 作用下， 生成 2-[Methoxy(diphenyl)methyl]cyclopent-2-en-1-ol
  参考文献：
  名称：

  Photochemical Generation and Methanol Trapping of Localized 1,3 and 1,4 Singlet Diradicals Derived from a Spiroepoxy-Substituted Cyclopentane-1,3-diyl

  摘要：

  The direct and benzophenone-sensitized photodenitrogenation of the azoalkane 2,3-diazabicyclo-[2.2.1]hept-2-ene-7,3'-spiro-2',2'-diphenyloxirane 1 at ambient temperature (ca. 15 OC) in benzene afforded exclusively the 6-oxabicyclo[3.2.0]hept-1-ene 3. The labile oxetane 3 is proposed to be formed by the selective cleavage of the C-O bond in the epoxy ring of the initially photogenerated, spiroepoxy-substituted, localized cyclopentane-1,3-diyl diradical 1,3-DR to the 1,4-DR diradical and subsequent cyclization of the latter. Even at -100 degrees C, the highly strained (strain energy estimated to be ca. 94 kcal/mol) spiroepoxy housane 2 could not be observed by H-1 NMR (600 MHz) spectroscopy. In MeOH, instead of the oxetane 3, the two regioisomeric MeOH adducts 6 (trapping product of the diradicals 1,3-DR and 1,4-DR) and 6' (methanolysis product of 3) were obtained in high yields. For the first time methanol trapping of a cyclopentane-1,3-diyl singlet diradical was achieved; the required dipolar character is presumably induced in this symmetric species by the polar methanol medium. Computational work (UB3LYP/6-31G*) reveals that the S-1,3-DR singlet diradical possesses a singlet ground state (Delta E-ST ca. 1 kcal/mol), for which ring closure (E-A ca. 2.6 kcal/mol) to the spiroepoxy housane 2 requires more activation than epoxide-ring opening (E-A Ca. 0.7 kcal/mol); the T-1,3-DR triplet species ring-opens spontaneously (E-A Ca. 0 kcal/mol) to the corresponding T-1,4-DR. Stereoelectronic effects dictate the appropriate conformational alignment of the C-O bond with the radical p orbital in the 1,3-DR for the selective cleavage of the C-O rather than C-C bond in the epoxy ring.

  DOI：

  10.1021/ja9822761

文献信息

• Reaction of 7,7-diphenyl-6-oxabicyclo[3.2.0]hept-1-ene with ROH; controlling factors on the regioselectivity in the nucleophilic addition reaction
  作者：Manabu Abe、Takafui Minamoto、Yasunori Ino、Takanori Kawakami、Masatomo Nojima

  DOI：10.1016/s0040-4020(02)00700-7

  日期：2002.8

  ROH-induced decomposition of the strained 7,7-diphenyl-6-oxabicyclo[3.2.0]hept-1-ene 1 was investigated in detail. The selective formation of the endo double-bonded alkene 3 was observed for the reaction with H2O or MeOH. Alternatively, the reaction with hexafluoro-2-propanol or acetic acid exclusively afforded the exo double-bonded alkene 5. The dramatic ROH effect on the product distribution is rationalized

  详细研究了ROH诱导的应变的7​​,7-二苯基-6-氧杂双环[3.2.0]庚-1-烯1的分解。对于与H 2 O或MeOH的反应，观察到内在双键烯烃3的选择性形成。备选地，与六氟-2-丙醇或乙酸的反应仅得到外型双键烯烃5。在这项研究中，合理的ROH对产品分布的影响是合理的。应变能（SE = 41.3千卡/摩尔）-6-氧杂二环的[3.2.0]庚-1-烯在RHF / 6-31G计算*理论水平。
• Mechanism of an Alcohol-Trapping Reaction in the Direct and Benzophenone-Sensitized Photodenitrogenation of a Spiroepoxy-Substituted Azoalkane:  Solvent Effects and Stereochemical Deuterium Labeling
  作者：Manabu Abe、Waldemar Adam、Takafumi Minamoto、Yasunori Ino、Masatomo Nojima

  DOI：10.1021/jo026873o

  日期：2003.3.1

  has been assessed through alcohol-trapping reactions for which the effect of solvent acidity on the product distribution of the alcohol trapping products 2 versus 3 + 4 and stereochemical deuterium-labeling studies have been performed. The proposed mechanism for the solvent effect on the product ratio (2/3 + 4) reveals the importance of the hydrogen-bonded intermediates I1 and I2 in the trapping reactions;

  已通过醇捕获反应评估了2-螺氧基环氧-1,3-环戊烷-1,3-二基DR2的自旋态依赖性反应性，单峰对三重峰，溶剂酸度对产物的酸分布有影响。进行了酒精捕集产品2与3 + 4的对比以及立体化学氘标记研究。所提出的溶剂对产物比率（2/3 + 4）的影响机理揭示了氢键合中间体I1和I2在捕集反应中的重要性。立体化学氘标记结果阐明了醇所俘获的偶极结构。可以推断出偶极子DP1和DP2保留了环氧化物氧和氘原子之间的构型，用于直接光脱氮反应（单态），