1-(二甲基(苯基)甲硅烷基)丙烷-1-酮 | 128084-44-6

• 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: 1-(二甲基(苯基)甲硅烷基)丙烷-1-酮
• 英文名称: 1-(dimethyl(phenyl)silyl)propan-1-one
• 英文别名: 1-[Dimethyl(phenyl)silyl]propan-1-one
• CAS: 128084-44-6
• 化学式: C₁₁H₁₆OSi
• 分子量: 192.333
• InChiKey: HROBBQKVBVKESN-UHFFFAOYSA-N

物化性质

• 沸点：
  83-86 °C(Press: 1.1 Torr)
• 密度：
  0.93±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.12
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-(二甲基(苯基)甲硅烷基)丙烷-1-酮 在 正丁基锂 、 乙基溴化镁 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 4.0h， 生成 dimethyl(nona-3,4-dien-3-yloxy)(phenyl)silane
  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
• 作为产物：
  描述：

  苯基二甲基氯硅烷 在 lithium 作用下， 以 四氢呋喃 为溶剂， 反应 41.5h， 生成 1-(二甲基(苯基)甲硅烷基)丙烷-1-酮
  参考文献：
  名称：

  使用吗啉酰胺可高效合成酰基硅烷。

  摘要：

  [反应：见正文]描述了由相应的吗啉酰胺和甲硅烷基锂物质合成酰基硅烷的一般方法。吗啉酰胺的使用是经济的，并防止了甲硅烷基亲核试剂的过度加成。该方法干净地以高收率提供了酰基硅烷，并且避免了通常用于从酰氯合成这些化合物的化学计量的氰化亚铜（I）的使用。

  DOI：

  10.1021/ol0483854

文献信息

• Enantioselective Synthesis of Chiral 3-Substituted-3-silylpropionic Esters <i>via</i> Rhodium/Bisphosphine-Thiourea-Catalyzed Asymmetric Hydrogenation
  作者：Zongpeng Zhang、Zhengyu Han、Guoxian Gu、Xiu-Qin Dong、Xumu Zhang

  DOI：10.1002/adsc.201700355

  日期：2017.8.7

  We have successfully developed the asymmetric hydrogenation of β‐silyl‐α,β‐unsaturated esters to prepare chiral 3‐substituted‐3‐silylpropionic ester products catalyzed by rhodium/bisphosphine‐thiourea (ZhaoPhos) with excellent results (up to 97% yield, >99% ee, 1500 TON). Moreover, our hydrogenation products can be efficiently converted to other important organic molecules, such as chiral ethyl (R

  我们已经成功开发出β-甲硅烷基-α，β-不饱和酯的不对称氢化反应，以制备铑/双膦-硫脲（ZhaoPhos）催化的手性3-取代-3-甲硅烷基丙酸酯产品，收率极佳（高达97％ee > 99％，1500吨）。此外，我们的加氢产物可以有效地转化为其他重要的有机分子，例如手性乙基（R）-3-羟基-3-苯基丙酸酯或（R）-3- [二甲基（苯基）甲硅烷基] -3-苯基丙酸。
• <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。
• Asymmetric Allylboration of Acylsilanes
  作者：John D. Buynak、Bolin Geng、Shinian Uang、J.Byron Strickland

  DOI：10.1016/s0040-4039(00)79945-x

  日期：1994.2

  Asymmetric allylboration of acylsilanes with B-allyldiisopinocampheylborane [(+)-Ipc2BAII] is highly substrate dependent, resulting in variable amounts of asymmetric induction. The determination of enantiomeric excess of the resulting highly hindered tertiary silylcarbinols was accomplished by reaction with diazaphospholidine 6 in the presence of a catalytic amount of methoxyacetic acid.

  酰基硅烷与B-烯丙基异硫代樟脑硼烷[（+）-Ipc 2 BAII]的不对称烯丙基硼化高度依赖于底物，导致可变数量的不对称诱导。在催化量的甲氧基乙酸的存在下，通过与二氮磷吡啶6反应来完成对所得的高度受阻的叔甲硅烷基甲醇的对映体过量的测定。
• Highly stereoselective syntheses of alkenylsilanes and germanes utilizing cyclobutyl ketones
  作者：Tooru Fujiwara、Koichi Sawabe、Takeshi Takeda

  DOI：10.1016/s0040-4020(97)00541-3

  日期：1997.6

  (E)-Alkenylsilanes were synthesized with high stereoselectivity by the diastereoselective addition of the dimethylphenylsilyllithium to the trans-2-phenylthiocyclobucyl ketones and the Lewis acid-promoted stereospecific ring opening reactions of the resulting cyclobutanemethanol derivatives. (E)- 1,5-Disubstituted-1, 5-dienylsilanes and germanes were also produced stereoselectively by the similar zinc salt-catalyzed ring opening reaction of alpha-dimethylphenylsilyl- or alpha-triethylgermyl-1-[2-(trimethylsilyl-methyl)cyclobutane]methanol derivatives. (C) 1997 Elsevier Science Ltd.

  (E)-alkenylsilanes 以高立体选择性合成，通过双相选择性加成二甲基芳香硅锂到转位-2-甲基环状单环三硫氰酸dehydes，以及配位酸促进行成的环状断裂反应所合成的环状乙醇二甲基交联产物。类似地，锌盐催化的环状断裂反应也能生产以高立体选择性合成(E)-1,5-二取代-1,5-二烯基硅烷和rades。该研究发表于1997年荷兰爱思 wer 出版社。
• Thiazolium-Catalyzed Additions of Acylsilanes:  A General Strategy for Acyl Anion Addition Reactions
  作者：Anita E. Mattson、Ashwin R. Bharadwaj、Andrea M. Zuhl、Karl A. Scheidt

  DOI：10.1021/jo060699c

  日期：2006.7.1

  utilizing N-heterocyclic carbenes (NHCs) derived from thiazolium salts has been developed for the generation of carbonyl anions from acylsilanes. Synthetically useful 1,4-diketones and N-phosphinoyl-α-aminoketones have been prepared in good to excellent yields via NHC-catalyzed additions of acylsilanes to the corresponding α,β-unsaturated systems and N-phosphinoylimines. These organocatalytic reactions

  已经开发出一种利用衍生自噻唑鎓盐的N-杂环卡宾（NHC）的策略，用于从酰基硅烷生成羰基阴离子。合成有用的1,4-二酮和N-膦酰基-α-氨基酮是通过NHC催化将酰基硅烷添加到相应的α，β-不饱和体系和N中来制备的，具有良好至优异的收率-膦基嘧啶。这些有机催化反应是耐空气和耐水的方法，可进行稳健的羰基阴离子加成反应。另外，已经使用该羰基阴离子方法以一锅法有效地合成了多取代的芳族呋喃和吡咯。向反应中加入醇使该过程在噻唑鎓盐中具有催化作用。为了沿着提出的反应途径合成潜在的中间体，已经确定甲硅烷基化的噻唑鎓甲醇在适当的亲电试剂存在下经受标准反应条件时可以提供高收率的羰基阴离子加成产物。