1,1-bis<(benzyloxy)methyl>-3-methyl-4-<(trimethylsilyl)methylene>cyclopentane

• 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: 1,1-bis<(benzyloxy)methyl>-3-methyl-4-<(trimethylsilyl)methylene>cyclopentane
• 英文别名: 1,1-bis(benzyloxymethyl)-3-<(E)-(trimethylsilyl)methylene>-4-methylcyclopentane；1,1-bis[(benzyloxy)methyl]-3-[(E)-(trimethylsilyl)methylene]-4-methylcyclopentane；trimethyl-[(E)-[2-methyl-4,4-bis(phenylmethoxymethyl)cyclopentylidene]methyl]silane
• 化学式: C₂₆H₃₆O₂Si
• 分子量: 408.656
• InChiKey: VMZZHUGACWTNQQ-NCELDCMTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.64
• 重原子数：
  29
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  烯丙基丙二酸二乙酯 在 titanium(IV) isopropylate 、 盐酸 、 lithium aluminium tetrahydride 、 正丁基锂 、 CCl₂CuN^(2-)*2Li⁽¹⁺⁾ 、 异丙基氯化镁 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 生成 1,1-bis<(benzyloxy)methyl>-3-methyl-4-<(trimethylsilyl)methylene>cyclopentane
  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

• Iron-Mediated and -Catalyzed Metalative Cyclization of Electron-Withdrawing-Group-Substituted Alkynes and Alkenes with Grignard Reagents
  作者：Takeshi Hata、Shiro Sujaku、Naoki Hirone、Kirihiro Nakano、Junsuke Imoto、Haduki Imade、Hirokazu Urabe

  DOI：10.1002/chem.201101273

  日期：2011.12.16

  transformations. The amount of FeCl2 was reduced to catalytic levels (10 mol % relative to enyne), and catalytic cyclizations of this sort proceeded with yields comparable to those of the aforementioned stoichiometric reactions. The cyclization of diethyl (E,E)‐2,7‐nonadienedioate with a stoichiometric amount of FeCl2/4 tBuMgCl, followed by the addition of sBuOH as a proton source, afforded a mixture of 2‐(eth

  用由FeCl 2和t BuMgCl生成的铁试剂按比例处理乙基（E）-5,5-双[（苄氧基）甲基] -8-（N，N-二乙基氨基甲酰基）-2-辛基-7-酸酯的1：4（简称的FeCl 2 /4吨BuMgCl），得到乙基[4,4-双[（苄氧基）甲基] -2 - [（ë） - （N，N- -diethylcarbamoyl）亚甲基]环戊-1-基乙酸]，收率高。对相同的反应混合物进行氘代分解，得到双氘代产物乙基[4,4-双[（苄氧基）甲基] -2-[[ E）-（N，N-二乙基氨基甲酰基）氘代亚甲基]环戊-1-基]氘代乙酸盐，因此确认了相应的双金属中间体的存在。后者的中间体可以与卤素或醛反应以促进进一步的合成转化。FeCl 2的量减少到催化水平（相对于烯炔为10mol％），并且这种催化环化的产率与上述化学计量反应的产率相当。二的环化（ë，ê）-2,7- nonadienedioate用的FeCl化学计量量的2
• 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。
• 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.