(dimethylmethoxysilyl)trimethylsilylmethyllithium | 120086-03-5

• 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: (dimethylmethoxysilyl)trimethylsilylmethyllithium
• CAS: 120086-03-5
• 化学式: C₇H₁₉LiOSi₂
• 分子量: 182.339
• InChiKey: YNZNWLCXVVLDPF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.08
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (dimethylmethoxysilyl)trimethylsilylmethyllithium 在 丁酮 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 12.0h， 生成
  参考文献：
  名称：

  含有Si–O键的位阻单-和双-碳负离子的碱金属配合物

  摘要：

  氧桥接的硅取代的烷烃{（Me 3 Si）2 CH（SiMe 2）} 2 O（1）可以通过{（Me 3 Si）2 CH} Li与ClSiMe 2 OSiMe 2 Cl的反应来制备。在回流的THF中。类似地，{ {Me 3 Si）（Me 2 MeOSi）CH} Li与ClSiMe之间的反应很容易获得烷烃{（Me 3 Si）（Me 2 MeOSi）CH（SiMe 2 CH 2）} 2 （2）。2 CH 2 CH 2森达在相同条件下为2 Cl。化合物1与两当量的MeK反应生成聚合物络合物[[{（（Me 3 Si） 2 C（SiMe 2）} 2 O] K 2（OEt 2）] ∞ [ 5（OEt 2）]重结晶。用两个等价的任意一个对2进行处理梅里或MeK给出相应的络合物[{（Me 3 Si）（Me 2 MeOSi）C（SiMe 2 CH 2）} 2 Li] [Li（DME）3 ] [ 7（DME）3 ]和[{（Me

  DOI：

  10.1039/b510692c
• 作为产物：
  描述：

  (methoxydimethylsilyl)(trimethylsilyl)methane 、 叔丁基锂 生成 (dimethylmethoxysilyl)trimethylsilylmethyllithium
  参考文献：
  名称：

  MARINO, JOSEPH P.;KIM, MIN-WOO;LAWRENCE, R., J. ORG. CHEM., 54,(1989) N, C. 1784-1785

  摘要：

  DOI：

文献信息

• Synthesis of (+)-8a,9-secoartemisinin and related analogs
  作者：Mitchell A. Avery、Wesley K.M. Chong、George Detre

  DOI：10.1016/s0040-4039(00)98789-6

  日期：1990.1

  An efficient synthesis of (+)-8a,9-secoartemisinin 2, ring-D cleaved, tricyclic analog of (+)-artemisinin 1, has been accomplished. Dioxetane7, produced upon ozonolysis of vinyl-silane 5 in methanol, was intercepted with acid to provide the stable bicyclic peroxy-aldehyde9, which was readily converted to the title compound(s).

  （+）-8a，9-secoartemisinin 2（（+）-artemisinin 1的环D切割的三环类似物的有效合成已完成。乙烯基硅烷5在甲醇中臭氧分解后生成的二氧杂环丁烷7被酸截留，以提供稳定的双环过氧醛9，其易于转化为标题化合物。
• Synthesis and structures of some new types of lithium β-diketiminates
  作者：Xue-Hong Wei、James D. Farwell、Peter B. Hitchcock、Michael F. Lappert

  DOI：10.1039/b716888h

  日期：——

  of [LiCH(SiMe(3))(SiMe(2)OMe)}](8) with 2Me(2)C(CN)(2) yielded the amorphous [LiSi(Me)(2)((NCR)(2)CH)}](n) [R = C(Me)(2)CN] (4). From [LiN(SiMe(3))C(Bu(t))C(H)SiMe(3)}](2) (A) and 1,3- or 1,4-C(6)H(4)(CN)(2), with no apparent synergy between the two CN groups, the product was the appropriate (mu-C(6)H(4))-bis(lithium beta-diketiminate) 6 or 7. Reaction of [LiN(SiMe(3))C(Ph)=C(H)SiMe(3)}(tmeda)]

  由[Li CH（SiMe（3））SiMe（ OMe）（2）}]（无穷大）和2 PhCN。它们的不同之处在于，每个二酮亚胺基配体的β-C原子处的取代基是SiMe（3）（2）或H（3）。每个具有（i）中心Si-O-Si单元，（ii）Si（Me）片段N，N'-在分子内桥接每个β-二酮亚胺，和（iii）Li（thf）（2）部分N，N'-分子间桥接两个β-二酮（thf =四氢呋喃）。用2Me（2）C（CN）（2）处理[Li CH（SiMe（3））（SiMe（2）OMe）}]（8）得到无定形的[Li Si（Me）（2）（ （NCR）（2）CH）}]（n）[R = C（Me）（2）CN]（4）。由[Li N（SiMe（3））C（Bu（t））C（H）SiMe（3）}]（2）（A）和1,3-或1,4-C（6）H（ 4）（CN）（2），两个CN组之间没有明显的协同作用，产物为适当的（mu-C（6）H（4））-双（β-二酮锂）6或7。[Li
• Tricyclic analogues of artemisinin: synthesis and antimalarial activity of (+)-4,5-secoartemisinin and (–)-5-nor-4,5-secoartemisinin
  作者：Mitchell A. Avery、Wesley K. M. Chong、James E. Bupp

  DOI：10.1039/c39900001487

  日期：——

  Two ring-A cleaved analogues of the natural product artemisinin have been synthesized and examined for in vitro antimalarial activity.

  已合成了天然产物青蒿素的两个A环切割类似物，并检查了其体外抗疟活性。
• Synthesis and structures of crystalline lithium 1-azaallyls and a 1,3-diazaallyl derived from Li{CH(SiMe3)(SiMe3−n(OMe)n)} (n=1 or 2) and Li{CH(SiMe2OMe)2} and RCN (R=tBu, Ph, 2,5-Me2C6H3, or Ad)
  作者：Peter B. Hitchcock、Michael F. Lappert、Xue-Hong Wei

  DOI：10.1016/s0022-328x(03)00433-9

  日期：2003.10
• Synthesis and structures of four crystalline lithium β-diketiminates derived from [Li{CH(SiMe3)(SiMe2OMe)}]8 and PhCN or ButCN and PhCN
  作者：Peter B. Hitchcock、Michael F. Lappert、Xue-Hong Wei

  DOI：10.1016/j.jorganchem.2004.01.011

  日期：2004.4

  Treatment at ambient temperature in diethyl ether of one equivalent of [LiCH(SiMe3)(SiMe2OMe)}](8) (A) with (i) two equivalents of PhCN, or (ii) successive equivalent portions of (BuCN)-C-l and PhCN gave from (i) [Li(OEt2)NSiMe2C(Ph)C(H)C(Ph)N}](4) (1) and [Li(OEt2)NSiMe2C(Ph)C(SiMe3)C(Ph)N}](2) (2) as well as the known lithium 1-azaallyl [LiN(SiMe2OMe)C(Ph)CH(SiMe3)}](3), and from (ii) [Li(THF)NSiMe2C(Bu-t)C(H)C(Ph)N}](4) (3) The latter was also obtained from the known [Li N(SiMe2OMe)C(Bu-t)CH(SiMe3)}](2) and PhCN under similar conditions. Recrystallisation of 2 from THF/hexane afforded [Li(THF)NSiMe2C(Ph)C(SiMe3)C(Ph)N}](4) (2'). X-ray diffraction data on 2, 2' and 3 are presented; data for 1 were only adequate to confirm its gross tetrameric structure. The particularly novel feature of these transformations of the lithium alkyl A into lithium beta-diketiminates 1, 2, 2' or 3 is that while the first 1,3-carbon to nitrogen shift from the alpha-carbon of A is both silicotropic and regiospecific (in so far as SiMe2OMe > SiMe3 in migratory aptitude), the second migration is indiscriminate: silicotropy yielding 1 or 3 but prototropy giving 2 (or T). Consistent with these observations. the central carbon atom of the beta-diketiminato ligand has significant carbanionic character in 2 or 2', attributed to its stabilisation by the exocyclic Me2sSi at C2. whereas in I or 3 there is pi-delocalisation. (C) 2004 Elsevier B.V. All rights reserved.