1-hydroxy-1-<3-(trimethylsilyl)-2-propynyl>cyclohexane | 79015-63-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-hydroxy-1-<3-(trimethylsilyl)-2-propynyl>cyclohexane
• 英文别名: 1-<(trimethylsilyl)propargyl>cyclohexan-1-ol；1-hydroxy-1-(3-trimethylsilylprop-2-ynyl)cyclohexane；1-(3-(trimethylsilyl)prop-2-ynyl)cyclohexanol；1-[3-(Trimethylsilyl)prop-2-yn-1-yl]cyclohexan-1-ol；1-(3-trimethylsilylprop-2-ynyl)cyclohexan-1-ol
• CAS: 79015-63-7
• 化学式: C₁₂H₂₂OSi
• 分子量: 210.392
• InChiKey: GBFFZZZSCNEOSM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.95
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-hydroxy-1-<3-(trimethylsilyl)-2-propynyl>cyclohexane 在 sodium hydride 作用下， 以 乙醇 、 苯 为溶剂， 反应 27.0h， 生成 O-<1-<3-(trimethylsilyl)prop-2-yn-1-yl>cyclohex-1-yl> Se-phenyl selenocarbonate
  参考文献：
  名称：

  Synthesis of .gamma.- and .delta.-lactones by free-radical annelation of Se-phenyl selenocarbonates

  摘要：

  A general method for the synthesis of gamma- and delta-lactones through the intramolecular addition of alkoxycarbonyl radicals, formed by reaction of Se-phenylselenocarbonates with n-Bu3SnH, onto carbon-carbon multiple bonds is described. This free-radical cyclization is characterized by high regioselectivity favoring exo addition and by a high ratio of cyclization to reduction. Monocyclic, fused bicyclic, and spirocyclic lactones are formed in good to excellent yield. Use of allyltri-n-butyltin as a chain-transfer agent in the place of n-Bu3SnH affords the corresponding 3-butenyl lactones.

  DOI：

  10.1021/jo00043a030
• 作为产物：
  描述：

  3-溴-1-三甲基硅基-1-丙炔 在 正丁基锂 、 水 作用下， 反应 6.0h， 生成 1-hydroxy-1-<3-(trimethylsilyl)-2-propynyl>cyclohexane
  参考文献：
  名称：

  Application of elementoorganic compounds of 15th and 16th Groups in organic synthesis. 100. Reactions of carbonyl compounds with [(trimethylsilyl)propargyl]diisobutyltelluronium bromide mediated by different strong bases: highly regioselective synthesis of (trimethylsilyl)propargyl alcohols and highly stereoselective synthesis of cis-(trimethylsilyl)alkynyl epoxides

  摘要：

  [(Trimethylsilyl)propargyl)]diisobutyltelluronium bromide (1), after being treated with alkyl- or aryllithium reagent, undergoes a lithium-tellurium exchange reaction via an unstable transient tetraorganyltellurium intermediate, and the in situ generated lithium species reacts with carbonyl compounds to give (trimethylsilyl)propargyl alcohols 2 in high yields with high regioselectivity. However, when the telluronium salt 1 was treated with nonnucleophilic bases such as LDA or lithium 2,2,6,6-tetramethylpiperidide, the moderately stabilized silylated telluronium ylide formed. The silylated telluronium ylide reacted with carbonyl compounds to afford (trimethylsilyl) alkynyl epoxides 11 in good to excellent yields with high cis stereoselectivity.

  DOI：

  10.1021/jo00050a042

文献信息

• Gallium-mediated highly regioselective reactions of trimethylsilylpropargyl bromide and trimethylsilylallyl bromide with carbonyl compounds
  作者：Ying Han、Yao-Zeng Huang

  DOI：10.1016/s0040-4039(00)78562-5

  日期：1994.12

  One-pot reactions of gallium powder, trimethylsilylpropargyl bromide, aldehydes or ketones in the presence of KI and LiCl show very high acetylenic selectivity and under the same conditions, trimethylsilylallyl bromide also exhibits very high selectivity favoring α-adducts.

  镓粉，三甲基甲硅烷基炔丙基溴，醛或酮在KI和LiCl存在下的一锅反应显示出很高的炔属选择性，在相同条件下，三甲基甲硅烷基烯丙基溴也表现出非常高的选择性，有利于α加合物。
• Palladium(II)-catalyzed formation of γ-butyrolactones from 4-trimethylsilyl-3-alkyn-1-ols: Synthetic and mechanistic aspects
  作者：Philippe Compain、Jacques Goré、Jean-Michel Vatèle

  DOI：10.1016/0040-4020(96)00567-4

  日期：1996.7

  γ-butyrolactones are obtained in good yields from 4-trimethylsilyl-3-alkyn-1-ols via Wacker-type oxidation reaction. A mechanism is proposed for this transformation: it involves two successive trans-hydroxypalladations followed by a [PdXSiMe3] syn-elimination and explains why the presence of the silyl group is essential in such a process.

  γ-丁内酯可以通过Wacker型氧化反应从4-三甲基甲硅烷基-3-炔基-1-醇中以高收率获得。提出了用于该转化的机理：其涉及两个连续的反式-羟基palladation，然后是[PdXSiMe 3 ]顺式消除，并解释了为什么在这样的过程中必须存在甲硅烷基。
• Silanes in organic syuthesis. 11. Regiocontrolled synthesis of α-hydroxymethylated (trimethylsilyl)allenes
  作者：Rhys G. Daniels、Leo A. Paquette

  DOI：10.1016/s0040-4039(01)90382-x

  日期：1981.1

  The organometallic produced by reaction of trimethylsilylpropargyl bromide with aluminum amalgam in anhydrous tetrahydrofuran condenses readily with aldehydes and ketones to give allenic alcohols resulting from coupling α to the trimethylsilyl substituent.

  由三甲基甲硅烷基炔丙基溴与铝汞齐在无水四氢呋喃中反应制得的有机金属容易与醛和酮缩合，得到烯丙醇，其由α与三甲基甲硅烷基取代基偶合而成。
• Synthesis of 3-silyl-2(5 H )-furanone by rhodium-catalyzed cyclocarbonylation
  作者：Yukimasa Fukuta、Isamu Matsuda、Kenji Itoh

  DOI：10.1016/s0040-4039(00)02234-6

  日期：2001.2

  of propargyl alcohol derivatives bearing a trialkylsilyl group on the terminal sp-carbon under hydroformylation conditions. The following two requirements must be satisfied for the success of this protocol; (i) the presence of a silyl group on the sp-carbon, and (ii) the presence of a catalytic amount of Rh4(CO)12.

  3-甲硅烷基- 2（5 ħ） -呋喃酮可容易地通过炔丙醇衍生物轴承三烷基甲硅烷基上的终端的铑催化cyclocarbonylation形成SP的加氢甲酰化条件下，碳上。为了使该协议成功，必须满足以下两个要求；（i）sp-碳上存在甲硅烷基，和（ii）催化量的Rh 4（CO）12存在。
• Selective multiple methylene insertion reactions mediated by iodomethylzine iodide: Mechanistic considerations and synthetic applications
  作者：Michael J. Rozema、Paul Knochel

  DOI：10.1016/s0040-4039(00)85980-8

  日期：1991.4

  The reaction of alkynylcoppers 1 with an excess of iodomethylzinc iodide selectively furnishes the quadruple methylene insertion copper organometallics 2 in fair to good yields. The mechanism of the reaction has been investigated and postulated intermediates such as 4 or 8 have been trapped with electrophiles like aldehydes or ketones in excellent yields. A new in situ preparation of propargylic copper

  炔基铜1与过量的碘代甲基碘化锌的反应选择性地以公平至良好的产率提供了四重亚甲基插入铜有机金属化合物2。已经研究了反应的机理，并且假定的中间体（如4或8）已被亲电子试剂（如醛或酮）以优异的产率捕获。已经开发了一种新的就地制备炔丙基铜衍生物4的方法，该方法从易于获得的炔铜化合物开始，从而以80-95％的收率制得了均炔丙基醇。