(diethylamino)diphenylsilyllithium | 140438-35-3

• 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: (diethylamino)diphenylsilyllithium
• 英文别名: lithium;diethylamino(diphenyl)silanide
• CAS: 140438-35-3
• 化学式: C₁₆H₂₀NSi*Li
• 分子量: 261.368
• InChiKey: AAFAIKCXIMLIFR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.86
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (diethylamino)diphenylsilyllithium 在 12-冠醚-4 、 氯化铵 作用下， 以 四氢呋喃 为溶剂， 反应 42.0h， 生成 三硅烷,2,2-二甲基-1,3-二(1-甲基乙氧基)-1,1,3,3-四苯基-
  参考文献：
  名称：

  The first stable functional silyl anions: (aminosilyl)lithiums

  摘要：

  DOI：

  10.1021/ja00036a064
• 作为产物：
  描述：

  chloro(N,N-diethylamino)diphenylsilane 在 lithium 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以100%的产率得到(diethylamino)diphenylsilyllithium
  参考文献：
  名称：

  官能化甲硅烷基阴离子的合成应用：氨基甲硅烷基阴离子作为羟基阴离子当量

  摘要：

  （氨基甲硅烷基）锂和相应的铜和镁试剂通过以下方式充当羟基阴离子当量：（1）烯丙基取代;（2）加入乙烯基环氧乙烷;和（3）加入乙炔，然后氧化裂解碳-碳键。在所有情况下都实现了高度区域和立体选择性转化。

  DOI：

  10.1016/0040-4020(96)00212-8

文献信息

• Mixed reagent (aminosilyl)lithium/i-PrMgBr for the synthesis of functionalized oligosilanes
  作者：Atsushi Kawachi、Kohei Tamao

  DOI：10.1016/s0022-328x(00)00077-2

  日期：2000.4

  Mixed reagents prepared in situ from the (aminosilyl)lithiums with i-PrMgBr undergo coupling reactions with chloro-oligosilanes without SiSi bond cleavage, which is a serious side reaction with the (aminosilyl)lithiums themselves. Based on the coupling reaction and the amino-to-chloro transformation, functionalized tetrasilanes and hexasilanes are synthesized. The analysis of the 1H- and 29Si-NMR

  由具有（I -PrMgBr ）的（氨基甲硅烷基）锂原位制备的混合试剂会与氯代低聚硅烷发生偶联反应，而没有SiSi键断裂，这是与（氨基甲硅烷基）锂本身的严重副反应。基于偶联反应和氨基到氯的转化，合成了官能化的四硅烷和六硅烷。所述的分析1 H-和29的Si-NMR谱表明，这些低聚包括三个构型异构体，LL，UL，和UU。
• Total synthesis of (+)-pramanicin and stereochemical elucidation of the natural product
  作者：Anthony G. M. Barrett、Marie L. Smith、Nicholas S. Stock

  DOI：10.1039/a807988i

  日期：——

  Total synthesis of (+)-pramanicin is achieved through a ‘one pot’ Michael addition of an aminosilyl zincate species to an α,β-unsaturated lactam and quenching of the resultant enolate with an α,β-unsaturated γ,δ-epoxy aldehyde.

  (+)-pramanicin 的全合成是通过氨硅锌酸盐与 α、β-不饱和内酰胺的 "一锅式 "迈克尔加成，以及用 α、β-不饱和 γ、δ-环氧醛淬灭生成的烯醇来实现的。
• The first catalytic asymmetric total synthesis of ent-hyperforin
  作者：Yohei Shimizu、Shi-Liang Shi、Hiroyuki Usuda、Motomu Kanai、Masakatsu Shibasaki

  DOI：10.1016/j.tet.2010.05.086

  日期：2010.8

  ent-hyperforin was described here in detail. Keys to the success were a catalytic asymmetric Diels–Alder reaction, a stereoselective Clasien rearrangement, an intramolecular aldol cyclization, and a vinylogous Pummerer rearrangement. Along with the successful synthetic route, several attempted approaches toward the construction of bicyclo[3.3.1] core and the C2 oxidation were discussed.

  对羟基丁香酚的第一个催化不对称全合成在此进行了详细描述。成功的关键是催化不对称Diels-Alder反应，立体选择性Clasien重排，分子内醛醇环化和乙烯基Pummerer重排。除了成功的合成路线外，还讨论了几种尝试构建双环[3.3.1]核和C2氧化的方法。
• Fleming−Tamao Oxidation and Masked Hydroxyl Functionality:  Total Synthesis of (+)-Pramanicin and Structural Elucidation of the Antifungal Natural Product (−)-Pramanicin
  作者：Anthony G. M. Barrett、John Head、Marie L. Smith、Nicholas S. Stock、A. J. P. White、D. J. Williams

  DOI：10.1021/jo9905672

  日期：1999.8.1

  The total synthesis of (+)-pramanicin (41b) is reported, thereby establishing the relative and absolute stereochemistry of the naturally occurring antifungal agent. The key steps involve (i) conjugate addition of the diethyl((diethylamino)diphenylsilyl)zincate to a suitably protected gamma-lactam 3 and quenching of the resultant enolate with the alpha,beta-unsaturated gamma,delta-epoxy aldehyde 2 (X = H), (ii) Ni(acac)(2)-catalyzed hydroxylation of a beta-dicarbonyl array, and (iii) Fleming-Tamao oxidation to reveal the masked C-3 hydroxyl group.
• Diastereoselective Heteroatom-Directed Conjugate Addition of Silylcuprate Reagents to Unsaturated Carbonyls. A Stereoselective Route to .beta.-Carbonyl Siloxanes1
  作者：Michael R. Hale、Amir H. Hoveyda

  DOI：10.1021/jo00095a007

  日期：1994.8

  Directed conjugate addition of the silylcuprate reagent lithium bis[diphenyl(diethylamino)silyl]-cuprate ((Ph(2)(Et(2)N)Si)(2)CuLi) to unsaturated esters and ketones is reported. The stereochemical course of the reaction can be-controlled by the presence of an appropriately disposed internal Lewis basic functionality, affording the corresponding beta-hydroxysilyl carbonyls with good to excellent levels of diastereoselection (e.g., 3b --> 4b).