1-烯丙基-2-亚甲基环戊烷甲醛 | 152705-48-1

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机氧化物
• 中文名称: 1-烯丙基-2-亚甲基环戊烷甲醛
• 英文名称: Cyclopentanecarboxaldehyde, 2-methylene-1-(2-propenyl)-(9CI)
• 英文别名: 2-methylidene-1-prop-2-enylcyclopentane-1-carbaldehyde
• CAS: 152705-48-1
• 化学式: C₁₀H₁₄O
• 分子量: 150.221
• InChiKey: VWFBNCLJAWOGEI-UHFFFAOYSA-N

物化性质

• 沸点：
  199.1±29.0 °C(Predicted)
• 密度：
  0.91±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  1-烯丙基-2-亚甲基环戊烷甲醛 在 2,6-二甲基吡啶 、 锌 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 生成 1-allyl-1-<1'-(tert-butyldimethylsiloxy)-3'-butynyl>-2-methylenecyclopentane
  参考文献：
  名称：

  Palladium-catalyzed cyclizations of polyenynes. A palladium zipper

  摘要：

  The cycloisomerization of polyenynes with a catalyst derived from Pd(0), acetic acid, and a ligand to polycycles depends upon the juxtaposition of unsaturation. The process involves the stages of initiation (by addition of Pd-H to an acetylene), propagation (by intramolecular carbopalladation), and termination (by beta-hydrogen elimination). With 2-homopropargylated 1,5- and 1,6-dienes, monocyclizations via 5-exo and 6-endo modes dominate with the ratio dependent upon ligand. The 5-exo mode is favored by tri-o-tolylphosphine, whereas triphenylstibine favors the 6-endo mode. On the other hand, a 3-homoallyl-3-homopropargylcyclopentene undergoes smooth bicyclization even when triphenylphosphine is used as ligand. Combining Pd(0)-catalyzed allylic alkylation to make the substrates with Pd(0)-catalyzed cycloisomerization simplifies triquinane and azatriquinane synthesis. A2-allyl-2-homopropargyl-1-methylenecycloalkane array cycloisomerizes to [4.3.3]propellanes and [3.3.3]propellanes. Methallyl alcohol serves as a basic building block to construct acyclic substrates for construction of spirocycles. Both terminal and internal acetylenes serve as suitable initiators provided the proper ligand is employed. With a terminal acetylene as initiator, triphenylphosphine proves satisfactory, but an internal acetylene requires triphenylstibine. High diastereoselectivity may accompany formation of the spirocycle. Increasing the number of double bonds increases the number of rings formed. Substrates bearing 3, 4, 5, 6, and 7 double bonds generate polyspiranes consisting of 3, 4, 5, 6, and 7 rings. The regio- and diastereoselectivity may be understood on the basis of a conformational analysis of the reactive intermediate. This atom economical approach for construction of polycycles can be considered as the equivalent of a palladium zipper in which the pi orbitals are the teeth and the palladium complex is the tab. Closing the zipper stitches the pi bonds into sigma bonds with creation of the polycycles.

  DOI：

  10.1021/ja00074a008
• 作为产物：
  描述：

  2-甲氧羰基环戊酮 在 lithium aluminium tetrahydride 、 草酰氯 、 四氯化钛 、 sodium hydride 、 二甲基亚砜 、 三乙胺 、 锌 作用下， 以 四氢呋喃 为溶剂， 反应 0.75h， 生成 1-烯丙基-2-亚甲基环戊烷甲醛
  参考文献：
  名称：

  Palladium-catalyzed cyclizations of polyenynes. A palladium zipper

  摘要：

  The cycloisomerization of polyenynes with a catalyst derived from Pd(0), acetic acid, and a ligand to polycycles depends upon the juxtaposition of unsaturation. The process involves the stages of initiation (by addition of Pd-H to an acetylene), propagation (by intramolecular carbopalladation), and termination (by beta-hydrogen elimination). With 2-homopropargylated 1,5- and 1,6-dienes, monocyclizations via 5-exo and 6-endo modes dominate with the ratio dependent upon ligand. The 5-exo mode is favored by tri-o-tolylphosphine, whereas triphenylstibine favors the 6-endo mode. On the other hand, a 3-homoallyl-3-homopropargylcyclopentene undergoes smooth bicyclization even when triphenylphosphine is used as ligand. Combining Pd(0)-catalyzed allylic alkylation to make the substrates with Pd(0)-catalyzed cycloisomerization simplifies triquinane and azatriquinane synthesis. A2-allyl-2-homopropargyl-1-methylenecycloalkane array cycloisomerizes to [4.3.3]propellanes and [3.3.3]propellanes. Methallyl alcohol serves as a basic building block to construct acyclic substrates for construction of spirocycles. Both terminal and internal acetylenes serve as suitable initiators provided the proper ligand is employed. With a terminal acetylene as initiator, triphenylphosphine proves satisfactory, but an internal acetylene requires triphenylstibine. High diastereoselectivity may accompany formation of the spirocycle. Increasing the number of double bonds increases the number of rings formed. Substrates bearing 3, 4, 5, 6, and 7 double bonds generate polyspiranes consisting of 3, 4, 5, 6, and 7 rings. The regio- and diastereoselectivity may be understood on the basis of a conformational analysis of the reactive intermediate. This atom economical approach for construction of polycycles can be considered as the equivalent of a palladium zipper in which the pi orbitals are the teeth and the palladium complex is the tab. Closing the zipper stitches the pi bonds into sigma bonds with creation of the polycycles.

  DOI：

  10.1021/ja00074a008

文献信息

• Barry M. Trost, Yian Shi, J. Amer. Chem. Soc, 115 (1993) N 21, S 9421-9438
  作者：Barry M. Trost, Yian Shi

  DOI：——

  日期：——
• Palladium-catalyzed cyclizations of polyenynes. A palladium zipper
  作者：Barry M. Trost、Yian Shi

  DOI：10.1021/ja00074a008

  日期：1993.10

  The cycloisomerization of polyenynes with a catalyst derived from Pd(0), acetic acid, and a ligand to polycycles depends upon the juxtaposition of unsaturation. The process involves the stages of initiation (by addition of Pd-H to an acetylene), propagation (by intramolecular carbopalladation), and termination (by beta-hydrogen elimination). With 2-homopropargylated 1,5- and 1,6-dienes, monocyclizations via 5-exo and 6-endo modes dominate with the ratio dependent upon ligand. The 5-exo mode is favored by tri-o-tolylphosphine, whereas triphenylstibine favors the 6-endo mode. On the other hand, a 3-homoallyl-3-homopropargylcyclopentene undergoes smooth bicyclization even when triphenylphosphine is used as ligand. Combining Pd(0)-catalyzed allylic alkylation to make the substrates with Pd(0)-catalyzed cycloisomerization simplifies triquinane and azatriquinane synthesis. A2-allyl-2-homopropargyl-1-methylenecycloalkane array cycloisomerizes to [4.3.3]propellanes and [3.3.3]propellanes. Methallyl alcohol serves as a basic building block to construct acyclic substrates for construction of spirocycles. Both terminal and internal acetylenes serve as suitable initiators provided the proper ligand is employed. With a terminal acetylene as initiator, triphenylphosphine proves satisfactory, but an internal acetylene requires triphenylstibine. High diastereoselectivity may accompany formation of the spirocycle. Increasing the number of double bonds increases the number of rings formed. Substrates bearing 3, 4, 5, 6, and 7 double bonds generate polyspiranes consisting of 3, 4, 5, 6, and 7 rings. The regio- and diastereoselectivity may be understood on the basis of a conformational analysis of the reactive intermediate. This atom economical approach for construction of polycycles can be considered as the equivalent of a palladium zipper in which the pi orbitals are the teeth and the palladium complex is the tab. Closing the zipper stitches the pi bonds into sigma bonds with creation of the polycycles.