methylene-7-(p-tolylsulfonyl)-7-aza-5,1-decen-9-yne | 131760-90-2

• 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: methylene-7-(p-tolylsulfonyl)-7-aza-5,1-decen-9-yne
• 英文别名: 4-methyl-N-(2-methylidenehex-5-enyl)-N-prop-2-ynylbenzenesulfonamide
• CAS: 131760-90-2
• 化学式: C₁₇H₂₁NO₂S
• 分子量: 303.425
• InChiKey: VWOPBAPHOTWTSE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  21
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  45.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methylene-7-(p-tolylsulfonyl)-7-aza-5,1-decen-9-yne 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 溶剂黄146 、 三(邻甲基苯基)磷 作用下， 以 苯 为溶剂， 反应 10.0h， 以88.7%的产率得到1,7-bis(methylene)-3-(p-tolylsulfonyl)-3-azaspiro<4.4>nonane
  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：

  Carbonic acid methyl ester 2-methylene-hex-5-enyl ester 在 苯磺酰胺 、 tris(dibenzylideneacetone)dipalladium (0) 、 sodium hydride 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 生成 methylene-7-(p-tolylsulfonyl)-7-aza-5,1-decen-9-yne
  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

• Tandem Cyclopropanation/Ring-Closing Metathesis of Dienynes
  作者：Brian P. Peppers、Steven T. Diver

  DOI：10.1021/ja049079o

  日期：2004.8.1

  cyclorearrangement by tandem cyclopropanation/ring-closing alkene metathesis, triggered by either a ruthenium carbene or noncarbene ruthenium(II) precatalyst. The process represents a variation of enyne metathesis where presumed cyclopropyl carbene intermediates undergo a consecutive ring-closing metathesis. A mechanistic proposal is offered, and sequential use of catalysts provided a tandem ring-closing enyne/alkene

  某些二炔通过串联环丙烷化/闭环烯烃复分解产生环重排，由钌卡宾或非卡宾钌 (II) 预催化剂触发。该过程代表烯炔复分解的变体，其中假定的环丙基卡宾中间体经历连续的闭环复分解。提供了一种机械建议，并且催化剂的顺序使用提供了串联闭环烯炔/烯烃复分解产物。
• Enantioselective Syntheses of Various Chiral Multicyclic Compounds with Quaternary Carbon Stereocenters by Catalytic Intramolecular Cycloaddition
  作者：Takanori Shibata、Yu-ki Tahara、Kohei Tamura、Kohei Endo

  DOI：10.1021/ja0762083

  日期：2008.3.1

  The intramolecular cycloaddition of 1,n-diene-ynes (n = 4-6), where alkyne and alkene moieties are connected by a 1,1-disubstituted alkene, was examined using a chiral rhodium catalyst, and various types of cycloadducts with quaternary carbon stereocenter(s) were obtained in high to excellent enantiomeric excess. In the case of 1,4-diene-ynes, tricyclic, bicyclic, and spirocyclic compounds were obtained depending upon the substituents at the 2-position of the 1,4-diene moiety and those at their alkyne termini. On the other hand, 1,5- and 1,6-diene-ynes gave tricyclic and bicyclic compounds, which included medium-sized ring systems. The mechanistic considerations for different reaction pathways and the synthetic transformation of tricyclic products into functionalized spirocyclic compounds are also described. The reaction of enediynes, where two alkyne moieties are connected by a 1,1-disubstituted alkene, was also examined, and sterically strained tricyclic compounds with two carbon stereocenters were obtained.
• A palladium-catalyzed zipper reaction
  作者：Barry M. Trost、Yian Shi

  DOI：10.1021/ja00002a064

  日期：1991.1
• 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：——