7-(tert-Butyl-dimethyl-silanyloxy)-hept-1-en-4-ol | 303014-95-1

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 7-(tert-Butyl-dimethyl-silanyloxy)-hept-1-en-4-ol
• 英文别名: 7-[tert-butyl(dimethyl)silyl]oxyhept-1-en-4-ol
• CAS: 303014-95-1
• 化学式: C₁₃H₂₈O₂Si
• 分子量: 244.45
• InChiKey: VKPZLNYIGPDYSI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.73
• 重原子数：
  16.0
• 可旋转键数：
  7.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  29.46
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  7-(tert-Butyl-dimethyl-silanyloxy)-hept-1-en-4-ol 在 正丁基锂 、 四丁基氟化铵 、 sodium hydride 作用下， 以 四氢呋喃 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.25h， 生成 (4E)-1-allyl-5-phenyl-4-pentenyl benzyl ether
  参考文献：
  名称：

  Relative Rate Profile for Ring-Closing Metathesis of a Series of 1-Substituted 1,7-Octadienes as Promoted by a 4,5-Dihydroimidazol-2-ylidene-Coordinated Ruthenium Catalyst

  摘要：

  GraphicsThis report details the kinetic responses of nine compounds of type 6 to ring-closing metathesis as promoted by 2 to give the identical product 7. The experimental observations have been subjected to Hammett analysis. The rho value for the composite aromatic derivatives (R = p-XC6H4-) differs from that of the aliphatic series, although both are negative because electron-donating groups accelerate the reaction.

  DOI：

  10.1021/ol0272794
• 作为产物：
  描述：

  ethyl 4-(t-butyldimethylsiloxy)butanoate 在 二异丁基氢化铝 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 1.5h， 生成 7-(tert-Butyl-dimethyl-silanyloxy)-hept-1-en-4-ol
  参考文献：
  名称：

  Relative Rate Profile for Ring-Closing Metathesis of a Series of 1-Substituted 1,7-Octadienes as Promoted by a 4,5-Dihydroimidazol-2-ylidene-Coordinated Ruthenium Catalyst

  摘要：

  GraphicsThis report details the kinetic responses of nine compounds of type 6 to ring-closing metathesis as promoted by 2 to give the identical product 7. The experimental observations have been subjected to Hammett analysis. The rho value for the composite aromatic derivatives (R = p-XC6H4-) differs from that of the aliphatic series, although both are negative because electron-donating groups accelerate the reaction.

  DOI：

  10.1021/ol0272794

文献信息

• Synthesis of <i>Z</i>-Alkenes from Rh(I)-Catalyzed Olefin Isomerization of β,γ-Unsaturated Ketones
  作者：Lian-Gang Zhuo、Zhong-Ke Yao、Zhi-Xiang Yu

  DOI：10.1021/ol401607c

  日期：2013.9.20

  Developing olefin isomerization reactions to reach kinetically controlled Z-alkenes is challenging because formation of trans-alkenes is thermodynamically favored under the traditional catalytic conditions using acids, bases, or transition metals as the catalysts. A new synthesis of Z-alkenes from Rh(I)-catalyzed olefin isomerization of β,γ-unsaturated ketones to α,β-unsaturated ketones was developed

  发展烯烃异构化反应以达到动力学控制的Z-烯烃是具有挑战性的，因为在使用酸，碱或过渡金属作为催化剂的传统催化条件下，热力学上有利于反式烯烃的形成。开发了一种由Rh（I）催化的将β，γ-不饱和酮异构化为α，β-不饱和酮的新方法合成Z-烯烃的方法，为获得各种Z-烯酮提供了一种简便而有效的方法。
• Chemo- and stereoselective six-membered oxonium ylide formation–[2,3]-sigmatropic rearrangement of 2-diazo-3-ketoesters with dirhodium(II) catalyst and its application to the synthesis of (+)-tanikolide
  作者：Hikari Jinnouchi、Hisanori Nambu、Kanae Takahashi、Tomoya Fujiwara、Takayuki Yakura

  DOI：10.1016/j.tet.2019.03.012

  日期：2019.4

  Dirhodium(II)-catalyzed oxonium ylide formation–[2,3]-sigmatropic rearrangement of 6-allyloxy-2-diazo-3-ketoesters possessing a C-6 substituent is described. The reaction of 6-alkyl- or 6-aryl-substituted 6-allyloxy-2-diazo-3-ketoesters with a catalytic amount of Rh2(S-PTTL)4 proceeded in a chemoselective and stereoselective manner to provide 6-substituted 2-allyl-3-oxotetrahydropyran-2-carboxylates

  描述了具有C-6取代基的Dirhodium（II）催化的氧鎓叶立德形成-[2,3]-σ重排的6-烯丙氧基-2-重氮-3-酮酸酯。6-烷基或6-芳基取代的6-烯丙氧基-2-重氮-3-酮酸酯与催化量的Rh 2（S -PTTL）4的反应以化学选择性和立体选择性方式进行，以提供6-取代的2 -烯丙基-3-氧代四氢吡喃-2-羧酸酯的收率高，非对映选择性高。为了证明该顺序反应的实用性，我们进行了（+）-tanikolide的全合成，其中δ-内酯骨架的构建是通过使用2-碘联苯甲酰胺催化的四氢吡喃-2-甲醇的氧化裂解而实现的。
• Cp₂TiCl₂-Catalyzed Photoredox Allylation of Aldehydes with Visible Light
  作者：Andrea Gualandi、Francesco Calogero、Martino Mazzarini、Simone Guazzi、Andrea Fermi、Giacomo Bergamini、Pier Giorgio Cozzi

  DOI：10.1021/acscatal.0c00348

  日期：2020.3.20

  A Barbier-type Cp2TiCl2-mediated (10 mol %) photoredox allylation of aldehydes under irradiation with visible light (blue light-emitting diodes (LEDs), 450 nm) and in the presence of an organic dye (3DPAFIPN, 5 mol %) with allylbromides is described.