1,6,11-tris(4-methylphenylsulfonyl)-1,6,11-triazaundeca-3,8-diyne

• 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: 1,6,11-tris(4-methylphenylsulfonyl)-1,6,11-triazaundeca-3,8-diyne
• 英文别名: 4-methyl-N-[4-[(4-methylphenyl)sulfonyl-[4-[(4-methylphenyl)sulfonylamino]but-2-ynyl]amino]but-2-ynyl]benzenesulfonamide
• 化学式: C₂₉H₃₁N₃O₆S₃
• 分子量: 613.78
• InChiKey: TWCSASBGHKWMLB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  41
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  155
• 氢给体数：
  2
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  1,6,11-tris(4-methylphenylsulfonyl)-1,6,11-triazaundeca-3,8-diyne 在 tris(triphenylphosphine)rhodium(l) chloride 、 potassium carbonate 作用下， 以 甲苯 、 乙腈 为溶剂， 反应 34.17h， 生成
  参考文献：
  名称：

  RhI催化的ne烯和and烯对映体的分子内[2 + 2 + 2]环加成反应：实验和理论机理研究

  摘要：

  令人满意地合成了N-甲苯磺酰基连接的开链炔-烯二烯1和2以及炔-烯二烯3和4。用上述底物测试了由威尔金森催化剂[RhCl（PPh 3）3 ]催化的[2 + 2 + 2]环加成过程，从而产生了高收率的环加合物。对映体1和2进行标准的[2 + 2 + 2]环加成反应，而对映体3和4进行β-氢化物消除，然后通过威尔金森催化剂还原消除，得到环加合物，该环加合物是通过标准[2 + 2 + 2]环加成反应获得的异构体。密度泛函理论计算已合理化了这两种烯二炔的不同反应性。

  DOI：

  10.1002/chem.201102210
• 作为产物：
  描述：

  N-(4-bromobut-2-yn-1-yl)-N-(tert-butoxycarbonyl)p-toluenesulfonamide 在 potassium carbonate 、 三氟乙酸 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 生成 1,6,11-tris(4-methylphenylsulfonyl)-1,6,11-triazaundeca-3,8-diyne
  参考文献：
  名称：

  RhI催化的ne烯和and烯对映体的分子内[2 + 2 + 2]环加成反应：实验和理论机理研究

  摘要：

  令人满意地合成了N-甲苯磺酰基连接的开链炔-烯二烯1和2以及炔-烯二烯3和4。用上述底物测试了由威尔金森催化剂[RhCl（PPh 3）3 ]催化的[2 + 2 + 2]环加成过程，从而产生了高收率的环加合物。对映体1和2进行标准的[2 + 2 + 2]环加成反应，而对映体3和4进行β-氢化物消除，然后通过威尔金森催化剂还原消除，得到环加合物，该环加合物是通过标准[2 + 2 + 2]环加成反应获得的异构体。密度泛函理论计算已合理化了这两种烯二炔的不同反应性。

  DOI：

  10.1002/chem.201102210

文献信息

• Fused tetracycles with a benzene or cyclohexadiene core: [2 + 2 + 2] cycloadditions on macrocyclic systems
  作者：Sandra Brun、Lídia Garcia、Iván González、Anna Torrent、Anna Dachs、Anna Pla-Quintana、Teodor Parella、Anna Roglans

  DOI：10.1039/b806524a

  日期：——

  A series of fused tetracycles with a benzene or cyclohexadiene core (2a–h) is satisfactorily prepared by intramolecular [2 + 2 + 2] cycloadditions of triynic and enediynic macrocycles (1a–h) under RhCl(PPh3)3 catalysis; the enantioselective cycloaddition of macrocycles1b and 1e gives chiral tetracycles with moderate enantiomeric excess.

  通过RhCl(PPh3)3催化下的内环[2 + 2 + 2]环加成反应，成功合成了以苯或环己二烯为核心的一系列融合四环化合物（2a–h），该化合物来源于三炔和烯炔大环（1a–h）。其中，大环1b和1e的手性选择性环加成反应生成了具有中等对映体过量值的手性四环化合物。
• New Unsaturated Azamacrocyclic Enediynes: Synthesis, Structural Analysis and Thermal Behavior
  作者：Anna Roglans、Ivan González、Jordi Benet-Buchholz、Pere Roura

  DOI：10.1055/s-2006-951511

  日期：2006.11

  The reaction of a bispropargyl bromide enediyne with several bis-NH-sulfonamide nucleophiles permits the easy synthesis of 14- and 19-membered macrocyclic enediynes. The new nitrogen-containing unsaturated macrocycles are fully characterized. The thermal reactivity of the new cyclic enediyne derivatives is investigated by means of differential scanning calorimetry (DSC).

  双丙炔溴烯二炔与几种双-NH-磺酰胺亲核试剂的反应可以轻松合成 14 元和 19 元大环烯二炔。新的含氮不饱和大环化合物已得到充分表征。通过差示扫描量热法（DSC）研究了新型环烯二炔衍生物的热反应性。
• Transition Metal-Mediated Intramolecular [2+2+2] Cycloisomerizations of Cyclic Triynes and Enediynes
  作者：Anna Torrent、Iván González、Anna Pla-Quintana、Anna Roglans、Marcial Moreno-Mañas、Teodor Parella、Jordi Benet-Buchholz

  DOI：10.1021/jo048056p

  日期：2005.3.1

  11-triazacyclopentadeca-3-ene-8,13-diynes (4 and 5) were satisfactorily prepared. [2+2+2] cycloisomerization processes catalyzed by transition metals were tested in the above-mentioned macrocycles. Readily available and familiar cyclotrimerization precatalysts were examined for efficiency. Among them, the RhCl(CO)(PPh3)2 complex was found to catalyze the cycloisomerization reaction giving the desired

  含氮的15元三乙炔大环化合物，称为1,6,11-三（芳基磺酰基）-1,6,11-三氮杂环戊酮-3,8,13-三炔（1）和烯二酮大环化合物，称为1,6,11-tris令人满意地制备了（芳基磺酰基）-1,6,11-三氮杂环戊基-3-烯-8,13-二炔（4和5）。在上述大环化合物中测试了由过渡金属催化的[2 + 2 + 2]环异构化过程。检查了现成的和熟悉的环三聚预催化剂的效率。其中，发现RhCl（CO）（PPh 3）2络合物催化环异构化反应，以高收率得到所需的环加合物。
• Rates and Mechanism of Rhodium-Catalyzed [2+2+2] Cycloaddition of Bisalkynes and a Monoalkyne
  作者：Anna Dachs、Anna Torrent、Anna Pla-Quintana、Anna Roglans、Anny Jutand

  DOI：10.1021/om900544u

  日期：2009.10.26

  The mechanism of RhCl(PPh3)(3)-catalyzed [2+2+2] cycloaddition of alkynes is investigated in the case of the reaction of symmetrical diynes 1a and 1b with the monoalkyne 3 (HOCH2-C C-CH2OH), leading to highly substituted benzene derivatives in dichloromethane at 25 degrees C. The two main steps of the catalytic cycle are characterized. The intermediate rhodacyclopentadiene Rh-III complexes 2a and 2b (formed by oxidative coupling after the coordination of the diynes 1a and 1b to RhCl(PPh3)(2)) are characterized by cyclic voltammetry, conductivity measurements, P-31 NMR, and ESI-MS. The formation of complexes 2a and 2b (step A) and their further reactions with the monoalkyne 3, which deliver RhCl(PPh3)(3) and the final product (step B), are followed by means of electrochemical techniques that deliver kinetic data for the two successive separately investigated steps. From the relative values of the half-reaction times of step A (t(A1/2) = 650 and 75 s for 1a and 1b, respectively) and step (t(B1/2) = 130 and 680 s for 2a and 2b, respectively) determined under stoichiometric conditions, it emerges that step A (coordination of the two C C bonds of 1, followed by oxidative coupling) is rate-determining in the reaction involving 2a, whereas step B (reaction of the intermediate complexes 2 with the monoalkyne 3) is rate-determining in the reaction involving 1b. Kinetic data for the catalytic cycle of a RhCl(PPh3)(3)-catalyzed [2+2+2] cycloaddition of alkynes are thus presented for the first time.
• Rhodium(I)-Catalyzed [2 + 2 + 2] Cycloaddition Reactions of Triacetylenic 15-Membered Aza Macrocycles: A Comparative Structural Study
  作者：Sandra Brun、Anna Torrent、Anna Pla-Quintana、Anna Roglans、Xavier Fontrodona、Jordi Benet-Buchholz、Teodor Parella

  DOI：10.1021/om200927f

  日期：2012.1.9

  A variety of new nitrogen-containing 15-membered triacetylenic macrocycles with one or two alkyl substituents in a propargylic position have been efficiently synthesized and completely characterized. These macrocyclic systems undergo [2 + 2 + 2] cycloaddition reactions, leading to the corresponding fused tetracycles with a benzene core on treatment with Wilkinson's catalyst, [RhCl(PPh3)(3)]. The effects of alkyl chains have been evaluated on both the efficiency of the reaction and the conformational and structural analysis of the reactants.