1-Benzyloxy-5-trimethylsilanyl-pent-4-yn-2-ol | 115352-38-0

• 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-Benzyloxy-5-trimethylsilanyl-pent-4-yn-2-ol
• 英文别名: 1-Phenylmethoxy-5-trimethylsilylpent-4-yn-2-ol
• CAS: 115352-38-0
• 化学式: C₁₅H₂₂O₂Si
• 分子量: 262.424
• InChiKey: ONKOOUWPXYMXHB-UHFFFAOYSA-N

物化性质

• 沸点：
  349.6±37.0 °C(Predicted)
• 密度：
  1.005±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.84
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-Benzyloxy-5-trimethylsilanyl-pent-4-yn-2-ol 在 potassium carbonate 作用下， 以 甲醇 为溶剂， 反应 0.5h， 生成 (+/-)-1-benzyloxy-4-pentyn-2-ol
  参考文献：
  名称：

  钌催化的乙烯基硅烷的合成和交叉偶联作为烯烃的选择性选择方法：苄基二甲基甲硅烷基作为强大的乙烯基金属官能团。

  摘要：

  [反应：见正文]钌催化的炔烃氢化硅烷化或甲硅烷基炔烃Alder烯反应提供了进入苄基二甲基甲硅烷基（BDMS）取代烯烃的入口。BDMS-乙烯基硅烷通过温和的钯催化的交叉偶联进行了进一步的修饰，对介入的合成操作（包括甲硅烷基醚脱保护）表现出显着的稳定性。

  DOI：

  10.1021/ol034463w
• 作为产物：
  描述：

  烯丙基苄基醚 在 正丁基锂 、 三甲基铝 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 5.5h， 生成 1-Benzyloxy-5-trimethylsilanyl-pent-4-yn-2-ol
  参考文献：
  名称：

  Pentacoordinate Organoaluminum Chemistry:  Catalytic Efficiency of Me₃Al in the Epoxide Cleavage with Alkynyllithiums

  摘要：

  A new and highly effective catalytic method for epoxide alkynylations has been developed that involves the chelation-controlled alkylation of heterosubstituted epoxides with Me3Al via pentacoordinate organoalluminum complexes by taking advantage of the exceedingly high affinity of aluminum to oxygen. For example, reaction of epoxy ether, (l-benzyloxy)-3-butene oxide (1), in toluene with PhC=CLi under the influence of catalytic Me3Al (10 mol%) proceeded smoothly at O degrees C for 5 h to furnish the alkynylation product, l-(benzyloxy)-6-phenylhex-5-yn-3-ol, in 76% yield [cf. 3% without Me3Al catalyst; 78% with stoichiometric Me3Al under similar conditions]. This represents the first catalytic procedure for the amphiphilic alkylation of epoxides. The participation of pentacoordinate Me3Al complexes of epoxy ethers of type 1 is emphasized by comparing the reactivity with the corresponding simple epoxide, 5-phenyl-l-pentene oxide, which was not susceptible to nucleophile attack of PhC=CLi with catalytic Me3A1 under similar conditions. The pentacoordinate complex formation of Me3Al with epoxy ether 1 is characterized by low-temperature C-13 and Al-27 NMR spectroscopy. This approach is also applicable to the selective alkynylation of tosyl aziridines with adjacent ether functionality, which provides a promising method for amino alcohol synthesis.

  DOI：

  10.1021/ja9842464

文献信息

• Ruthenium-Catalyzed Vinylsilane Synthesis and Cross-Coupling as a Selective Approach to Alkenes:  Benzyldimethylsilyl as a Robust Vinylmetal Functionality
  作者：Barry M. Trost、Michelle R. Machacek、Zachary T. Ball

  DOI：10.1021/ol034463w

  日期：2003.5.1

  [reaction: see text] Ruthenium-catalyzed alkyne hydrosilylation or silyl-alkyne Alder ene reactions provide entry into benzyldimethylsilyl (BDMS)-substituted alkenes. The BDMS-vinylsilanes are further elaborated through mild palladium-catalyzed cross coupling and show significant stability to intervening synthetic operations, including silyl ether deprotection.

  [反应：见正文]钌催化的炔烃氢化硅烷化或甲硅烷基炔烃Alder烯反应提供了进入苄基二甲基甲硅烷基（BDMS）取代烯烃的入口。BDMS-乙烯基硅烷通过温和的钯催化的交叉偶联进行了进一步的修饰，对介入的合成操作（包括甲硅烷基醚脱保护）表现出显着的稳定性。
• Alkyne Hydrosilylation Catalyzed by a Cationic Ruthenium Complex:  Efficient and General Trans Addition
  作者：Barry M. Trost、Zachary T. Ball

  DOI：10.1021/ja0528580

  日期：2005.12.1

  The complex [Cp*Ru(MeCN)3]PF6 is shown to catalyze the hydrosilylation of a wide range of alkynes. Terminal alkynes afford access to alpha-vinylsilane products with good regioselectivity. Deuterium labeling studies indicate a clean trans addition process is at work. The same complex is active in internal alkyne hydrosilylation, where absolute selectivity for the trans addition process is maintained

  复合物 [Cp*Ru(MeCN)3]PF6 显示可催化多种炔烃的氢化硅烷化。末端炔烃可以提供具有良好区域选择性的 α-乙烯基硅烷产品。氘标记研究表明，清洁的反式添加过程正在发挥作用。相同的复合物在内部炔烃氢化硅烷化中具有活性，其中保持了反式加成过程的绝对选择性。几种内部炔烃底物类别，包括炔丙醇和 α,β-炔基羰基化合物，允许区域选择性乙烯基硅烷的形成。多种硅烷的耐受性值得注意，包括烷基硅烷、芳基硅烷、烷氧基硅烷和卤代硅烷。这种优势在用于硅系分子内 Diels-Alder 环加成反应的三烯底物的直接合成中得到了证明。
• Synthesis of a marine polyether toxin, okadaic acid [1] — strategy and synthesis of segment a
  作者：Yoshiyasu Ichikawa、Minoru Isobe、Dong-Lu Bai、Toshio Goto

  DOI：10.1016/s0040-4020(01)86915-5

  日期：1987.1

  The title compound was divided into three retrosynthetic segments A, B and C, by disconnecting two C-C bonds at C- and C-. Segment A for okadaic acid synthesis comprises the carbon skeleton from C-1 through C-14, which was further disconnected at the bonds between C-8 and C-9 into two fragments A1 and A2. Each fragment was synthesized in the optically active form from D-glucose derivatives. Key steps

  标题化合物，分为三个逆合成段A，B和C，通过断开在C- 2个CC键和C- 。冈田酸合成的链段A包含从C-1到C-14的碳骨架，该碳骨架在C-8和C-9之间的键处进一步断开成两个片段A 1和A 2。由D-葡萄糖衍生物以旋光形式合成每个片段。关键步骤是加氧汞化和抗选择性杂合物的加成，以修饰这些片段无环部分上的不对称碳。炔属碳负离子和各个片段的内酯羰基之间的偶联被促进。片段A以36个步骤合成。
• The silylalkyne-Prins cyclization: a novel synthesis of 4-iododihydropyrans
  作者：J.S. Yadav、N. Thrimurtulu、K. Anantha Lakshmi、A.R. Prasad、B.V. Subba Reddy

  DOI：10.1016/j.tetlet.2009.11.103

  日期：2010.1

  The silylated secondary homopropargylic alcohols undergo smooth coupling with aldehydes in the presence of molecular iodine under mild reaction conditions to produce 4-iododihydropyrans in good yields. This method is highly stereoselective, affording cis-dihydropyrans exclusively. (C) 2009 Elsevier Ltd. All rights reserved.
• Remarkable catalytic activity of Me3Ga in the alkylation of hetero-substituted epoxides with alkynyllithiums
  作者：Takashi Ooi、Junko Morikawa、Hayato Ichikawa、Keiji Maruoka

  DOI：10.1016/s0040-4039(99)01096-5

  日期：1999.8

  Regio- and stereoselective ring-opening reaction of hetero-substituted epoxides with alkynyllithiums can be catalyzed by Me3Ga with remarkable efficiency at 0 similar to 20 degrees C via pentacoordinate chelate-type complex. (C) 1999 Elsevier Science Ltd. All rights reserved.