(E)-11-phenyl-10-undecenal | 133100-37-5

• 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: (E)-11-phenyl-10-undecenal
• 英文别名: (E)-11-phenylundec-10-enal
• CAS: 133100-37-5
• 化学式: C₁₇H₂₄O
• 分子量: 244.377
• InChiKey: URUBUEOBMNWBIT-UKTHLTGXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  18
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (E)-11-phenyl-10-undecenal 在 正丁基锂 、 三苯基膦 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 1.5h， 生成 (E)-dodec-1-en-11-yn-1-ylbenzene
  参考文献：
  名称：

  Palladium-Catalyzed Isomerization of Aryl-Substituted Epoxides:  A Selective Synthesis of Substituted Benzylic Aldehydes and Ketones

  摘要：

  Aryl-substituted epoxides bearing multiple methyl substituents on the epoxide ring isomerize in the presence of 5 mol % Pd(OAc)(2)PR3 (R = n-Bu, Ph) to form the corresponding benzylic aldehyde or ketone, with complete regioselectivity for the carbonyl compound formed via cleavage of the benzylic C-O bond. No allylic alcohols or products arising from alkyl migration are observed. Rapid reaction rates and nearly quantitative yields are obtained, even with highly sterically hindered epoxides, using tri-n-butylphosphine as ligand and tert-butyl alcohol as solvent. 2-Aryl-substituted epoxides with two methyl substituents on C3 are completely unreactive, consistent with an oxidative addition/beta-hydride elimination mechanism. Catalyst variation studies show that both Pd(OAc)(2) and PR3 are essential for optimal activity and that palladium catalysts formed in this manner are superior to other Pd(O) catalysts (e.g., Pd(PPh3)(4)). The reactivity of catalytic Pd(OAc)(2)/PR3 toward multiply-substituted epoxides is compared to traditional Lewis acid catalysts; the former is found to be much more selective for isomerization without skeletal rearrangement. A mechanistic rationale involving turnover-limiting S(N)2-like attack of Pd(O) at the benzylic carbon is proposed.

  DOI：

  10.1021/jo970743b
• 作为产物：
  描述：

  10-十一烯醛 在 sodium hydroxide 、 硼烷四氢呋喃络合物 、 磷酸 、 Celite 、 双氧水 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 49.5h， 生成 (E)-11-phenyl-10-undecenal
  参考文献：
  名称：

  Palladium-Catalyzed Isomerization of Aryl-Substituted Epoxides:  A Selective Synthesis of Substituted Benzylic Aldehydes and Ketones

  摘要：

  Aryl-substituted epoxides bearing multiple methyl substituents on the epoxide ring isomerize in the presence of 5 mol % Pd(OAc)(2)PR3 (R = n-Bu, Ph) to form the corresponding benzylic aldehyde or ketone, with complete regioselectivity for the carbonyl compound formed via cleavage of the benzylic C-O bond. No allylic alcohols or products arising from alkyl migration are observed. Rapid reaction rates and nearly quantitative yields are obtained, even with highly sterically hindered epoxides, using tri-n-butylphosphine as ligand and tert-butyl alcohol as solvent. 2-Aryl-substituted epoxides with two methyl substituents on C3 are completely unreactive, consistent with an oxidative addition/beta-hydride elimination mechanism. Catalyst variation studies show that both Pd(OAc)(2) and PR3 are essential for optimal activity and that palladium catalysts formed in this manner are superior to other Pd(O) catalysts (e.g., Pd(PPh3)(4)). The reactivity of catalytic Pd(OAc)(2)/PR3 toward multiply-substituted epoxides is compared to traditional Lewis acid catalysts; the former is found to be much more selective for isomerization without skeletal rearrangement. A mechanistic rationale involving turnover-limiting S(N)2-like attack of Pd(O) at the benzylic carbon is proposed.

  DOI：

  10.1021/jo970743b

文献信息

• Photochemistry of 2-phenylcyclanones. Formation of cyclophanes and encapsulation by a ship-in-bottle and by a reptation strategy
  作者：Xue Gong. Lei、Charles E. Doubleday、Matthew B. Zimmt、Nicholas J. Turro

  DOI：10.1021/ja00269a051

  日期：1986.4

  The photochemistry of five- and six-membered cyclanones has played an important role in the development of mechanistic organic chemistry and in our knowledge of biradicals. The dominant primary photochemical process of these alkanones is homolytic ..cap alpha..-cleavage (type I process) of a T/sub 1/ (n,..pi..*) state which produces a triplet biradical. The latter is stabilized after intersystem crossing

  五元和六元气旋酮的光化学在机械有机化学的发展和我们对双自由基的了解中发挥了重要作用。这些烷酮的主要主要光化学过程是 T/sub 1/ (n,..pi..*) 状态的均裂 ..cap α..-裂解（I 型过程），产生三重双自由基。后者通过歧化反应（生成烯酮和/或烯醛）和组合反应（生成起始结构或异构体）在系统间交叉为单线态双自由基后稳定。例如，2-苯基环戊酮和2-苯基环己酮的光解以良好的产率产生链烯醛。我们报告说较大环旋风酮 (10, 11, 12, 和 15 名成员）通过以前未曾预料和史无前例的双自由基稳定组合过程产生对环烷。我们还报告说，光化学旋风酮到环烷烃的转化过程中发生的尺寸/形状变化可以用作瓶中船和爬行策略的基础，以不可逆地将有机分子封装在沸石的超级笼状空隙中。
• Photochemistry of large-ring 2-phenylcycloalkanones in various environments. Intramolecular para-coupling products of acyl benzyl biradicals
  作者：Nianhe Han、Xuegong Lei、Nicholas J. Turro

  DOI：10.1021/jo00008a065

  日期：1991.4
• LEI XUEGONG; DOUBLEDAY CH. , JR.; TURRO N. J., TETRAHEDRON LETT., 27,(1986) N 39, 4675-4678
  作者：LEI XUEGONG、 DOUBLEDAY CH. , JR.、 TURRO N. J.

  DOI：——

  日期：——
• JPH07173166A
  申请人：——

  公开号：JPH07173166A

  公开（公告）日：1995-07-11
• Palladium-Catalyzed Isomerization of Aryl-Substituted Epoxides:  A Selective Synthesis of Substituted Benzylic Aldehydes and Ketones
  作者：Sanjitha Kulasegaram、Robert J. Kulawiec

  DOI：10.1021/jo970743b

  日期：1997.9.1

  Aryl-substituted epoxides bearing multiple methyl substituents on the epoxide ring isomerize in the presence of 5 mol % Pd(OAc)(2)PR3 (R = n-Bu, Ph) to form the corresponding benzylic aldehyde or ketone, with complete regioselectivity for the carbonyl compound formed via cleavage of the benzylic C-O bond. No allylic alcohols or products arising from alkyl migration are observed. Rapid reaction rates and nearly quantitative yields are obtained, even with highly sterically hindered epoxides, using tri-n-butylphosphine as ligand and tert-butyl alcohol as solvent. 2-Aryl-substituted epoxides with two methyl substituents on C3 are completely unreactive, consistent with an oxidative addition/beta-hydride elimination mechanism. Catalyst variation studies show that both Pd(OAc)(2) and PR3 are essential for optimal activity and that palladium catalysts formed in this manner are superior to other Pd(O) catalysts (e.g., Pd(PPh3)(4)). The reactivity of catalytic Pd(OAc)(2)/PR3 toward multiply-substituted epoxides is compared to traditional Lewis acid catalysts; the former is found to be much more selective for isomerization without skeletal rearrangement. A mechanistic rationale involving turnover-limiting S(N)2-like attack of Pd(O) at the benzylic carbon is proposed.