α,α-d2-benzyltrimethylsilane | 78808-66-9

• 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: α,α-d2-benzyltrimethylsilane
• 英文别名: α,α-d₂-benzyltrimethylsilane
• CAS: 78808-66-9
• 化学式: C₁₀H₁₆Si
• 分子量: 166.307
• InChiKey: MRIWRLGWLMRJIW-KNXIQCGSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.11
• 重原子数：
  11.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  碘苯二乙酸 、 α,α-d2-benzyltrimethylsilane 在 三氟化硼乙醚 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 3.0h， 生成
  参考文献：
  名称：

  碘定向对位和邻位CH官能团的迭代碘合成的多取代碘芳烃的合成

  摘要：

  在卤代芳族化合物中，碘代芳烃的独特之处在于其能够产生稳定的卤素（III）形式。早些时候，这类碘（III）中心被证明可以通过卤素中心重排使C H官能化成邻位碘。通过测试不寻常的碘定向的对CH苄基化的程度，以及通过开发与磺酰基取代的烯丙基硅烷的高效CH偶联，可以探索这种现象的更广泛含义。通过偶合事件的单发性质和碘保留的结合，可以通过依次结合多达三个芳族CH位来制备多取代的芳烃。这种基于碘的迭代合成将用作形成增值芳烃核的工具。

  DOI：

  10.1002/anie.201809657
• 作为产物：
  描述：

  苯甲醇-Alpha,Alpha-d2 在 盐酸 、 magnesium 、 zinc(II) chloride 作用下， 反应 6.0h， 生成 α,α-d2-benzyltrimethylsilane
  参考文献：
  名称：

  SET and Exciplex Pathways in the Photochemical Reactions between Aromatic Ketones and Benzylsilane and Stannane Derivatives

  摘要：

  The photochemical reaction of alpha,alpha,alpha-trifluoroacetophenone (TFA), benzophenone, and p-cyanoacetophenone with benzyltrimethylsilane in MeCN involves hydrogen transfer from the benzylic position. Desilylation occurs as a minor process only in the case of TFA (but it increases greatly in the presence of MeOH or LiClO4). The final products result from the statistical recombination of the benzyl and ketyl radicals. Further cases of intramolecular selectivity studied are p-methylbenzyl- and p-methoxybenzyltrimethylsilane (the latter substrate undergoes mainly C-Si bond cleavage in the reaction with TFA) as well as benzyltributylstannane (only destannylation observed with all ketones). Product studies are complemented by the determination of relevant kinetic parameters through steady-state and flash-photolysis experiments. The results are explained in terms of hydrogen transfer proceeding from an exciplex and desilylation from the solvent separated radial ion pair. The latter species predominates when Delta G(et) < -10 kcal mol(-1).

  DOI：

  10.1021/ja00135a003

文献信息

• Cesium Amide‐Catalyzed Selective Deuteration of Benzylic C‐H Bonds with D ₂ and Application for Tritiation of Pharmaceuticals
  作者：Hui‐Zhen Du、Jun‐Zhen Fan、Zhong‐Zhen Wang、Neil A. Strotman、Haifeng Yang、Bing‐Tao Guan

  DOI：10.1002/anie.202214461

  日期：2023.2.13

  Cesium amide catalyst establishes a new bridge between benzylic C−H bonds and D2/T2, facilitating deuteration and tritiation of pharmaceutical compounds.

  铯酰胺催化剂在苄基 C−H 键和 D 2 /T 2之间建立了新的桥梁，促进了药物化合物的氘化和氚化。
• Rhodium-Catalyzed Silylation and Intramolecular Arylation of Nitriles via the Silicon-Assisted Cleavage of Carbon−Cyano Bonds
  作者：Mamoru Tobisu、Yusuke Kita、Yusuke Ano、Naoto Chatani

  DOI：10.1021/ja804992n

  日期：2008.11.26

  A rhodium-catalyzed silylation reaction of carbon-cyano bonds using disilane has been developed. Under these catalytic conditions, carbon-cyano bonds in aryl, alkenyl, allyl, and benzyl cyanides bearing a variety of functional groups can be silylated. The observation of an enamine side product in the silylation of benzyl cyanides and related stoichiometric studies indicate that the carbon-cyano bond cleavage proceeds through the deinsertion of silyl isocyanide from eta(2)-iminoacyl complex B. Knowledge gained from these studies has led to the development of a new intramolecular biaryl coupling reaction in which aryl cyanides and aryl chlorides are cross-coupled.