4,4-bis[(benzyloxy)methyl]-1,7-bis(trimethylsilyl)-1,6-heptadiyne | 169123-68-6

• 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: 4,4-bis[(benzyloxy)methyl]-1,7-bis(trimethylsilyl)-1,6-heptadiyne
• 英文别名: 4,4-bis(benzyloxymethyl)-1,7-bis(trimethylsilyl)-1,6-heptadiyne；4,4-bis[(benzyloxy)methyl]-1,7-bis(trimethylsilyl)indan；[4,4-Bis(phenylmethoxymethyl)-7-trimethylsilylhepta-1,6-diynyl]-trimethylsilane
• CAS: 169123-68-6
• 化学式: C₂₉H₄₀O₂Si₂
• 分子量: 476.806
• InChiKey: JMLNFANOMJSJTN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.95
• 重原子数：
  33
• 可旋转键数：
  12
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4,4-bis[(benzyloxy)methyl]-1,7-bis(trimethylsilyl)-1,6-heptadiyne 在 titanium(IV) isopropylate 、 diclazuril 、 异丙基氯化镁 作用下， 生成
  参考文献：
  名称：

  从1,6-或1,7-二烯，烯炔产生titanabicycles，和二炔和的合成的应用（ν 2 -丙烯）的Ti（O-我-Pr）2

  摘要：

  标题不饱和化合物和化学计量量的（ν 2 -丙烯）的Ti（ø -我-镨）2，得到titanabicycles，其中，在水解时，就给取代的环戊烷和环己烷框架。钛环也可以被氘，碘或一氧化碳拦截。

  DOI：

  10.1016/0040-4039(95)00727-t
• 作为产物：
  描述：

  2,2-dipropargyl-1,3-propandiol 在 正丁基锂 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 生成 4,4-bis[(benzyloxy)methyl]-1,7-bis(trimethylsilyl)-1,6-heptadiyne
  参考文献：
  名称：

  Aldehyde Addition and Copper-Mediated Allylation of Bicyclic Alkoxytitanacyclopentenes and -Pentadienes:  New Selectivities and an Unusual Reaction

  摘要：

  Bicyclic titanacyclopentenes generated in situ from 1,6-enynes and (eta(2)-propene)Ti(O-i-Pr)(2) (1) reacted with aldehydes at their alkenyl-titanium bond in the absence or presence of Ti(O-i-Pr)(n)Cl(4-n) (n = 2 or 3) to give allyl alcohols such as 5-7 as a nearly single stereoisomer in good yields. Upon workup with DCl/D(2)O or iodine, deuterio and iodo derivatives, 8 and 9, were obtained. Bicyclic titanacyclopentadienes prepared analogously from 1,6- or 1,7-diynes and 1 also reacted with aldehydes in the presence of an additional equivalent of Ti(O-i-Pr)(2)Cl(2) to afford 1,2-dialkylidenecyclopentanes pr -cyclohexanes having an alcohol moiety in their side chain in good yields. In place of the simple hydrolysis, deuteriolysis or iodinolysis gave the corresponding derivatives such as 21 or 22. Treatment of 1,6-enyne 10 with 1 in the standard way and then with a slight excess of i-PrMgCl at -50 degrees C generated a new titanium species that, upon reaction with aldehydes, afforded unexpected adducts 34 and 41-45 virtually as a single isomer. Copper-mediated allylation of dialkoxytitanacyclopentene such as 3 with allyl bromide proceeded at their vinyl-titanium bond to give 48 and 50. Likewise, dialkoxytitanacyclopentadiene prepared from 29 and 1 underwent the regioselective copper-mediated mono-allylation to give a 9:1 mixture of 53 and 54. Upon workup with deuteriochloric acid, the corresponding deuterated product was obtained with a high degree of deuterium incorporation.

  DOI：

  10.1021/ja982501e

文献信息

• Selective Preparation of Benzyltitanium Compounds by the Metalative Reppe Reaction. Its Application to the First Synthesis of Alcyopterosin A
  作者：Ryoichi Tanaka、Yoshitaka Nakano、Daisuke Suzuki、Hirokazu Urabe、Fumie Sato

  DOI：10.1021/ja027008o

  日期：2002.8.1

  divalent titanium alkoxide reagent, Ti(O-i-Pr)4/2 i-PrMgCl, reacted with propargyl bromide to give directly benzyltitanium compounds. The resultant benzyltitanium compounds underwent deuteriolysis, iodinolysis (with I2), or oxygenation (with O2 gas) to give the corresponding deuterium-labeled compounds, iodides, or alcohols, illustrating their synthetic versatility. The first synthesis of alcyopterosin A

  二烷氧基钛环戊二烯由两种不同的乙炔和二价钛醇盐试剂 Ti(Oi-Pr)4/2 i-PrMgCl 制备，与炔丙基溴反应直接得到苄基钛化合物。得到的苄基钛化合物经过氘分解、碘分解（用 I2）或氧化（用 O2 气体）得到相应的氘标记化合物、碘化物或醇，说明了它们的合成多功能性。alcyopterosin A 的首次合成，一种最近分离和表征的双环芳香倍半萜类化合物，已通过这种方法实现，从乙炔和二炔的适当组合开始。
• Selective Reaction of Aldehydes with Bicyclic Titanacyclopentadienes or Titanacyclopentenes Prepared <i>in Situ</i> from 1,6- or 1,7-Diynes or Enynes and<b> (</b>η²-Propene)Ti(O-<i>i</i>-Pr)₂
  作者：Hirokazu Urabe、Fumie Sato

  DOI：10.1021/jo961340z

  日期：1996.1.1
• Metalative Reppe Reaction. Organized Assembly of Acetylene Molecules on Titanium Template Leading to a New Style of Acetylene Cyclotrimerization
  作者：Daisuke Suzuki、Hirokazu Urabe、Fumie Sato

  DOI：10.1021/ja0161913

  日期：2001.8.1
• Aldehyde Addition and Copper-Mediated Allylation of Bicyclic Alkoxytitanacyclopentenes and -Pentadienes:  New Selectivities and an Unusual Reaction
  作者：Hirokazu Urabe、Fumie Sato

  DOI：10.1021/ja982501e

  日期：1999.2.1

  Bicyclic titanacyclopentenes generated in situ from 1,6-enynes and (eta(2)-propene)Ti(O-i-Pr)(2) (1) reacted with aldehydes at their alkenyl-titanium bond in the absence or presence of Ti(O-i-Pr)(n)Cl(4-n) (n = 2 or 3) to give allyl alcohols such as 5-7 as a nearly single stereoisomer in good yields. Upon workup with DCl/D(2)O or iodine, deuterio and iodo derivatives, 8 and 9, were obtained. Bicyclic titanacyclopentadienes prepared analogously from 1,6- or 1,7-diynes and 1 also reacted with aldehydes in the presence of an additional equivalent of Ti(O-i-Pr)(2)Cl(2) to afford 1,2-dialkylidenecyclopentanes pr -cyclohexanes having an alcohol moiety in their side chain in good yields. In place of the simple hydrolysis, deuteriolysis or iodinolysis gave the corresponding derivatives such as 21 or 22. Treatment of 1,6-enyne 10 with 1 in the standard way and then with a slight excess of i-PrMgCl at -50 degrees C generated a new titanium species that, upon reaction with aldehydes, afforded unexpected adducts 34 and 41-45 virtually as a single isomer. Copper-mediated allylation of dialkoxytitanacyclopentene such as 3 with allyl bromide proceeded at their vinyl-titanium bond to give 48 and 50. Likewise, dialkoxytitanacyclopentadiene prepared from 29 and 1 underwent the regioselective copper-mediated mono-allylation to give a 9:1 mixture of 53 and 54. Upon workup with deuteriochloric acid, the corresponding deuterated product was obtained with a high degree of deuterium incorporation.
• Synthetic application of titanabicycles generated from 1,6- or 1,7-dienes, enynes, and diynes and (ν2-propene)Ti(O-i-Pr)2
  作者：Hirokazu Urabe、Takeshi Hata、Fumie Sato

  DOI：10.1016/0040-4039(95)00727-t

  日期：1995.6

  The title unsaturated compounds and a stoichiometric amount of (ν2-propene)Ti(O-i-Pr)2 afforded titanabicycles, which, upon hydrolysis, gave substituted cyclopentane and cyclohexane frameworks. The titanacycles could be also intercepted with deuterium, iodine, or carbon monoxide.

  标题不饱和化合物和化学计量量的（ν 2 -丙烯）的Ti（ø -我-镨）2，得到titanabicycles，其中，在水解时，就给取代的环戊烷和环己烷框架。钛环也可以被氘，碘或一氧化碳拦截。