3-[二甲基(苯基)甲硅烷基]-1-苯基戊-1-炔-3-醇 | 918138-93-9

• 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
• 中文名称: 3-[二甲基(苯基)甲硅烷基]-1-苯基戊-1-炔-3-醇
• 英文名称: 3-(dimethyl(phenyl)silyl)-1-phenylpent-1-yn-3-ol
• 英文别名: 3-[Dimethyl(phenyl)silyl]-1-phenylpent-1-yn-3-ol；3-[dimethyl(phenyl)silyl]-1-phenylpent-1-yn-3-ol
• CAS: 918138-93-9；918139-10-3
• 化学式: C₁₉H₂₂OSi
• 分子量: 294.469
• InChiKey: TZILYYOKNRGIMS-UHFFFAOYSA-N

物化性质

• 沸点：
  404.6±40.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.33
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.26
• 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：

  3-[二甲基(苯基)甲硅烷基]-1-苯基戊-1-炔-3-醇 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 生成 (Z)-2-(hydroxy(phenyl)methyl)-1-phenylpent-1-en-3-one
  参考文献：
  名称：

  N-杂环卡宾引发的α-酰基乙烯基阴离子反应性：将α-羟基炔丙基硅烷添加到醛中。

  摘要：

  通过N-杂环卡宾引发的α-羟基炔丙基硅烷与醛的加成反应制备高度取代的α，β-不饱和酮。对于这些类型的化合物，该策略可作为标准Morita-Baylis-Hillman（MBH）方法的高效替代方案。与MBH反应相反，产物（R1）的β-位的不同取代可以以中等至优异的收率进行，并且高度控制所得的烯烃。

  DOI：

  10.1021/ol0710515
• 作为产物：
  描述：

  苯乙炔 、 1-(二甲基(苯基)甲硅烷基)丙烷-1-酮 在 乙基溴化镁 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 4.0h， 以55%的产率得到3-[二甲基(苯基)甲硅烷基]-1-苯基戊-1-炔-3-醇
  参考文献：
  名称：

  Stereoselective Lewis Acid-Catalyzed α-Acylvinyl Additions

  摘要：

  Silyloxyallenes derived from alpha-hydroxypropargylsilanes undergo efficient addition to aldehydes with catalytic amounts of Lewis acids. The allenes are accessed from the corresponding propargylsilanes in a base-catalyzed 1,2-Brook rearrangement/SE2' process. Enantioenriched propargylsilanes are synthesized by a new zinc-promoted addition of alkynes to acylsilanes in up to 74% ee. This work demonstrates that conversion to the silyloxyallenes occurs with minimal erosion in optical activity. The use of a chiral chromium(III) Lewis acid effects the catalytic asymmetric addition of racemic silyloxyallenes to aromatic aldehydes in up to 92% ee. The overall reaction is broad in scope and accommodates a wide variety of aromatic and aliphatic substituents on both the propargylsilane and aldehyde.

  DOI：

  10.1021/ja0653674

文献信息

• Highly Selective α-Acylvinyl Anion Additions to Imines
  作者：Troy E. Reynolds、Michael S. Binkley、Karl A. Scheidt

  DOI：10.1021/ol802227t

  日期：2008.11.20

  alpha-Hydroxypropargylsilanes undergo rearrangement to form reactive lithium allenolates. The resulting alpha-acylvinyl anion equivalents undergo highly selective additions to N-tert-butanesulfinyl imines generating beta-substituted aza-MBH-type products. High yields are achieved for a wide range of alpha-hydroxypropargylsilanes as well as for a diverse selection of imines. The reactions proceed with good

  α-羟基炔丙基硅烷会发生重排，形成反应性烯丙基锂。所得的α-酰基乙烯基阴离子当量经过高度选择性的加成反应，生成N-叔丁烷亚磺酰基亚胺，生成β-取代的氮杂-MBH型产物。对于广泛的α-羟基炔丙基硅烷以及各种亚胺选择，都可实现高收率。反应以良好的至优异的非对映选择性和区域选择性（8-20：1主链/ Sigma小链）进行，有利于烯烃的Z-异构体。
• <i>N</i>-Heterocyclic Carbene-Initiated α-Acylvinyl Anion Reactivity:  Additions of α-Hydroxypropargylsilanes to Aldehydes
  作者：Troy E. Reynolds、Charlotte A. Stern、Karl A. Scheidt

  DOI：10.1021/ol0710515

  日期：2007.6.1

  Highly substituted alpha,beta-unsaturated ketones are prepared by the N-heterocyclic carbene-initiated addition of alpha-hydroxypropargylsilanes to aldehydes. This strategy serves as a highly efficient alternative to the standard Morita-Baylis-Hillman (MBH) approaches for these types of compounds. In contrast to the MBH reaction, different substitution in the beta-position of the product (R1) can be accommodated

  通过N-杂环卡宾引发的α-羟基炔丙基硅烷与醛的加成反应制备高度取代的α，β-不饱和酮。对于这些类型的化合物，该策略可作为标准Morita-Baylis-Hillman（MBH）方法的高效替代方案。与MBH反应相反，产物（R1）的β-位的不同取代可以以中等至优异的收率进行，并且高度控制所得的烯烃。
• Stereoselective Lewis Acid-Catalyzed α-Acylvinyl Additions
  作者：Troy E. Reynolds、Ashwin R. Bharadwaj、Karl A. Scheidt

  DOI：10.1021/ja0653674

  日期：2006.12.1

  Silyloxyallenes derived from alpha-hydroxypropargylsilanes undergo efficient addition to aldehydes with catalytic amounts of Lewis acids. The allenes are accessed from the corresponding propargylsilanes in a base-catalyzed 1,2-Brook rearrangement/SE2' process. Enantioenriched propargylsilanes are synthesized by a new zinc-promoted addition of alkynes to acylsilanes in up to 74% ee. This work demonstrates that conversion to the silyloxyallenes occurs with minimal erosion in optical activity. The use of a chiral chromium(III) Lewis acid effects the catalytic asymmetric addition of racemic silyloxyallenes to aromatic aldehydes in up to 92% ee. The overall reaction is broad in scope and accommodates a wide variety of aromatic and aliphatic substituents on both the propargylsilane and aldehyde.