(±)-2-(dimethylphenylsilyl)-1-buten-3-ol | 129158-82-3

• 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: (±)-2-(dimethylphenylsilyl)-1-buten-3-ol
• 英文别名: 3-[dimethyl(phenyl)silyl]but-3-en-2-ol；3-(dimethylphenylsilyl)-3-buten-2-ol；3-Phenyldimethylsilylbut-3-en-2-ol
• CAS: 129158-82-3
• 化学式: C₁₂H₁₈OSi
• 分子量: 206.36
• InChiKey: CSMMEDRJEBLYGV-UHFFFAOYSA-N

物化性质

• 沸点：
  279.9±23.0 °C(Predicted)
• 密度：
  0.94±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.08
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  (±)-2-(dimethylphenylsilyl)-1-buten-3-ol 在 palladium diacetate 、 三苯基膦 吡啶 作用下， 以 二氯甲烷 为溶剂， 70.0 ℃ 、6.08 MPa 条件下， 反应 60.0h， 生成 (Z)-3-(Dimethyl-phenyl-silanyl)-pent-3-enoic acid methyl ester
  参考文献：
  名称：

  Palladium(0)-Catalyzed Carbonylation of 1-Alkyl-2-trialkylsilyl-2-propenyl Carbonates

  摘要：

  Pd(0)- 催化 1-烷基-2-三烷基硅烷-2-丙烯基碳酸甲酯的羰基化需要强制条件[CO（60 atm），70 °C]，以得到各自的(E)-3-三烷基硅烷-3-烯酸甲酯作为主要产物，以及(Z)-异构体和不同程度的不常见同分异构产物--2-烷基-3-三烷基硅烷-3-丁烯酸甲酯。

  DOI：

  10.1246/cl.1991.1993
• 作为产物：
  描述：

  二甲基苯基乙烯基硅烷 在 吡啶 、 溴 、 叔丁基锂 作用下， 以 四氯化碳 、 乙醚 、 正戊烷 为溶剂， 反应 16.17h， 生成 (±)-2-(dimethylphenylsilyl)-1-buten-3-ol
  参考文献：
  名称：

  Anderson, James C.; Smith, Stephen C.; Swarbrick, Martin E., Journal of the Chemical Society. Perkin transactions I, 1997, # 10, p. 1517 - 1521

  摘要：

  DOI：

文献信息

• PtCl2/XPhos: A highly efficient and readily available catalyst for the hydrosilylation of propargylic alcohols
  作者：Mark G. McLaughlin、Matthew J. Cook

  DOI：10.1039/c1cc14433b

  日期：——

  A highly regioselective hydrosilylation of propargylic alcohols has been developed using an in situ prepared PtCl(2)/XPhos catalyst system. The reaction is tolerant of many functional groups and exhibits excellent regio and geometric selectivity.

  使用原位制备的PtCl（2）/ XPhos催化剂系统开发了炔丙醇的高度区域选择性氢化硅烷化反应。该反应可耐受许多官能团，并具有出色的区域和几何选择性。
• Diastereoselective synthesis of substituted prolines via 5-endo-trig cyclisations of aza-[2,3]-Wittig sigmatropic rearrangement products
  作者：James C. Anderson、Elizabeth A. Davies

  DOI：10.1016/j.tet.2010.04.095

  日期：2010.8

  3]-Wittig sigmatropic rearrangement products from α-amino acid derivatives are susceptible to a rare nucleophilic 5-endo-trig cyclisations of an amine onto a non-conjugated vinylsilane in high yield and complete diastereocontrol. Five examples are presented, with cyclisation yields between 35 and 87%. A rationale for the stereoselectivity of the cyclisation is forwarded based upon the steric control factors

  的氮杂主要非对映体[2,3] -Wittigσ迁移重排产物从α氨基酸衍生物很容易受到亲核罕见5-内切- trig的胺的环化到以高收率和完整diastereocontrol非共轭乙烯基硅烷。给出了五个例子，环化产率在35％至87％之间。基于已针对aza- [2,3] -Wittigσ重排所记录的空间控制因素，提出了环化立体选择性的基本原理。还对反应条件下的机理进行了讨论。甲硅烷基被氧化成羟基并被完全去除已证明可用于合成。
• Allylsilanes in organic synthesis; convenient preparation of synthetic intermediates by catalytic hydrosilation of acetylenic alcohols
  作者：Patrick J. Murphy、John L. Spencer、Garry Procter

  DOI：10.1016/s0040-4039(00)94428-9

  日期：1990.1

  Synthetically useful vinylslane-alcohols such as (1) can be easily prepared by the catalytic hydrosilation of the appropriate acetylenic alcohols in high yield, and with excellent regioand stereoselectivity, without the need to protect the hydroxyl group.

  可通过合适的炔属醇的催化硅氢化作用以高收率，具有优异的区域选择性和立体选择性而无需保护羟基的情况下，容易地制备合成有用的乙烯基sl烷醇（如（1））。
• Titanocene-Mediated Homolytic Opening of Epoxysilanes
  作者：Nicolas Puljic、Matthias Albert、Anne-Lise Dhimane、Louis Fensterbank、Emmanuel Lacôte、Max Malacria

  DOI：10.1002/hlca.200690213

  日期：2006.10

  The titanocene(III) chloride mediated opening of silyloxiranes has been examined. Electron transfer from the metal leads to α-silyl radicals with total regiocontrol. The radicals could be trapped by various olefins, and the corresponding adducts were obtained in good yields (Table). Further substitution of the oxirane by alkyl groups proved detrimental to the reactions, but ring opening remained essentially

  已经检测了钛茂（III）氯化物介导的甲硅烷基氧杂环戊烷的打开。从金属的电子转移导致具有完全区域控制的α-甲硅烷基自由基。自由基可被各种烯烃捕获，并以高收率获得相应的加合物（表）。证明用烷基进一步取代环氧乙烷对反应是有害的，但是开环基本上保持区域选择性。
• Highly Regio- and Diastereoselective One-Pot Synthesis of Silyl Epoxy Alcohols and Vinylsilanes by Direct Hydroxy-Epoxidation
  作者：Waldemar Adam、Markus J. Richter

  DOI：10.1021/jo00091a021

  日期：1994.6

  A direct synthesis of silyl epoxy alcohols from vinyl silanes is described. It consists of the regioselective ene reaction of the vinylsilanes with singlet oxygen, which proceeds with predominant hydrogen abstraction at the position geminal to the silyl group. The resulting silyl allylic hydroperoxides were treated, without isolation, subsequently with Ti(O-i-Pr)(4) to afford the silyl epoxy alcohols in good yields and very high diastereomeric ratios, which ranged from 93:7 to greater than 97:3. Alternatively, the vinylsilanes were photooxygenated directly in the presence of the titanium catalyst and the silyl epoxy alcohols obtained in good yields. The method was applied to di- and trisubstituted acyclic vinylsilanes with a methyl group geminal to silicon and cyclic derivatives all give consistently good results. In this novel hydroxy-epoxidation, the regioselectivity of the singlet oxygen ene reaction as well as the diastereoselectivity of the oxygen transfer can be controlled by the steering effects of the silyl group.