methyl 4-(cyano(trimethylsilyloxy)methyl)benzoate | 93555-00-1

• 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: methyl 4-(cyano(trimethylsilyloxy)methyl)benzoate
• 英文别名: 4-[cyano(trimethylsilyloxy)methyl]benzoate；Methyl 4-[cyano(trimethylsilyloxy)methyl]benzoate
• CAS: 93555-00-1
• 化学式: C₁₃H₁₇NO₃Si
• mdl: MFCD17090867
• 分子量: 263.368
• InChiKey: KYRBFAWFBATXIB-UHFFFAOYSA-N

物化性质

• 沸点：
  332.5±32.0 °C(Predicted)
• 密度：
  1.071±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.07
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.384
• 拓扑面积：
  59.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl 4-(cyano(trimethylsilyloxy)methyl)benzoate 在 氨 作用下， 以 甲醇 为溶剂， 反应 2.0h， 生成 4-(Amino-cyano-methyl)-benzoic acid methyl ester; hydrochloride
  参考文献：
  名称：

  Facile synthesis of α-aminonitriles

  摘要：

  DOI：

  10.1016/s0040-4039(01)91205-5
• 作为产物：
  描述：

  三甲基氰硅烷 、 对甲酰基苯甲酸甲酯 在 碘 作用下， 以 二氯甲烷 为溶剂， 反应 0.05h， 以90%的产率得到methyl 4-(cyano(trimethylsilyloxy)methyl)benzoate
  参考文献：
  名称：

  碘催化中性条件下三甲基氰化甲硅烷加成羰基化合物

  摘要：

  在催化量的元素碘存在下，三甲基氰化甲硅烷与脂肪族或芳香族醛和酮的反应在很短的时间内以高产率产生了相应的氰醇三甲基甲硅烷基醚。

  DOI：

  10.1080/713744569

文献信息

• Catalytic cyanosilylation using germylene stabilized platinum(<scp>ii</scp>) dicyanide
  作者：Mahendra Kumar Sharma、Dharmendra Singh、Pritam Mahawar、Ravi Yadav、Selvarajan Nagendran

  DOI：10.1039/c8dt00043c

  日期：——

  The ability of a platinum compound to act as a catalyst for the cyanosilylation of carbonyl compounds is demonstrated through a well-defined germylene stabilized Pt(II) dicyanide, trans-(iBu)2ATIGe(iPr)}2Pt(CN)2.

  铂化合物充当羰基化合物的氰基甲硅烷基化反应的催化剂的能力已通过定义明确的亚甲基苯稳定的Pt（II）二氰化物，反式-（i Bu）2 ATIGe（i Pr）} 2 Pt（CN ）证明。）2。
• DMAP-Organocatalyzed <i>O</i>-Silyl-<i>O</i>-(or <i>C</i>-)-Benzoyl Interconversions by Means of Benzoyl Fluoride
  作者：Vincent Levacher、Thomas Poisson、Vincent Dalla、Cyril Papamicaël、Georges Dupas、Francis Marsais

  DOI：10.1055/s-2007-968028

  日期：2007.2

  A mild and efficient transprotection of alcohols from silyl ethers 1a-f to benzoates 2a-f is reported in fair to good yields (50-98%). This silyl-acyl exchange reaction proceeds readily in ­acetonitrile at room temperature in the presence of benzoyl fluoride and DMAP as an acyl transfer catalyst. A two-step ‘one-pot’ DMAP-catalyzed silylcyanation-transprotection sequence which gives the corresponding O-benzoyl cyanohydrines 2g-l in high yields (72-98%) from various benzaldehyde and ketone derivatives is also reported. This original organocatalytic acyl transfer process was also found to be effective in the O-benzoylation of trimethysilyl enolates 1m-o, providing enol esters 2m-o. Lastly, the potential of this strategy is also illustrated by a DMAP-mediated Claisen condensation between ketene silyl acetals 1p-r and benzoyl fluoride.

  本文报道了一种温和且高效的硅醚保护的醇（1a-f）向苯甲酸酯（2a-f）的转化反应，产率良好至优秀（50-98%）。该硅基-酰基交换反应在室温下，以乙腈为溶剂，在苯甲酰氟和DMAP作为酰基转移催化剂的存在下易于进行。同时，还报道了一种两步“一步法”DMAP催化硅氰化-转移保护序列，从各种苯甲醛和酮衍生物得到相应的O-苯甲酰氰醇（2g-l），产率高达72-98%。这种原创的有机催化酰基转移过程在O-苯甲酰化三甲基硅烯醇盐（1m-o）中同样有效，生成烯醇酯（2m-o）。最后，通过DMAP介导的烯酮硅缩醛（1p-r）与苯甲酰氟的Claisen缩合反应，也展示了该策略的应用潜力。
• Alkali metal complexes as efficient catalysts for hydroboration and cyanosilylation of carbonyl compounds
  作者：Adimulam Harinath、Jayeeta Bhattacharjee、Hari Pada Nayek、Tarun K. Panda

  DOI：10.1039/c8dt02032a

  日期：——

  N-adamantyliminopyrolyl ligand 2-(AdNCH)–C4H3NH (L–H) and alkali metal hexamethyldisilazides [MN(SiMe3)2] (M = Li, Na and K) to afford the dimeric [2-(AdNCH)–C4H3NLi(THF)}2] (1), [2-(AdNCH)–C4H3N}Na(THF)1.5}2] (2) and polymeric [2-(AdNCH)–C4H3NK(THF)}n] (3) complexes at ambient temperature. A one-pot reaction between L–H, [KN(SiMe3)2] and alkaline earth metal diiodide (AeI2) in a 2 : 2 : 1 molar ratio, which

  我们在这里报告N-金刚烷基吡咯基配体2-（AdN CH）–C 4 H 3 NH（L–H）与碱金属六甲基二硅叠氮化物[MN（SiMe 3）2 ]（M = Li，Na和K）之间的反应二聚体[2-（AdN CH）–C 4 H 3 NLi（THF）} 2 ]（1），[2-（AdN CH）–C 4 H 3 N} Na（THF）1.5 } 2 ] （2）和聚合的[2-（AdN CH）–C 4 H 3 NK（THF）} n ]（3）在环境温度下的配合物。L–H，[KN（SiMe 3）2 ]与碱土金属二碘化物（AeI 2）之间以2：2：1的摩尔比进行一锅反应，导致形成杂配Ae金属络合物[κ]还报告了2- 2-（AdN CH）–C 4 H 3 N} 2 Ae（THF）2 ] [Ae = Mg（4），Ca（5）]。复合物的固态结构1，3和4通过单晶X射线衍射分析来建立。碱金属和碱土金属配合物1-5被
• An uncoordinated tertiary nitrogen based tricarboxylate calcium network with Lewis acid–base dual catalytic sites for cyanosilylation of aldehydes
  作者：Ying-Xia Wang、Hui-Min Wang、Pan Meng、Dong-Xia Song、Juan-Juan Hou、Xian-Ming Zhang

  DOI：10.1039/d0dt03747h

  日期：——

  The design and utilization of dual sites for synergistic catalysts has been recognised as an efficient method towards high-efficiency catalysis in the cyanosilylation of aldehydes, which gives key intermediates for the synthesis of a number of valuable natural and pharmaceutical compounds. However, most of the reported dual-site catalysts for this reaction were homogeneous, accompanied by potential

  协同催化剂双位点的设计和利用已被认为是醛氰基化中高效催化的有效方法，它为合成许多有价值的天然和药物化合物提供了关键的中间体。然而，大多数报道的用于该反应的双中心催化剂是均相的，伴随着通过双中心的内部络合而可能失活。在这里，通过合理选择不配位的叔氮基三羧酸配体（三[（4-羧基）-苯基二氢基]胺，H 3 TCBPA），新的三维钙基金属-有机骨架（MOF），Ca 3（TCBPA）2（DMA）2（H 2 O）2（1，其中TCBPA =离子化的三[（4-羧基）-苯二甲基]胺，DMA = N，N-二甲基乙酰胺），具有易接近的双催化位点，路易斯碱性N和路易斯酸性Ca，由一锅溶剂热反应。如预期的那样，1在室温下能够双重和非均相催化醛的氰基硅烷化反应，并且可以重复使用至少6次，最大周转数（TON）为1301，优于大多数报道的案例。另外，1显示了CO 2的吸附能力和环氧化物的转化，这对建立可持续发展的社会是有益的。
• Three-Dimensional Co(II)-Metal–Organic Frameworks with Varying Porosities and Open Metal Sites toward Multipurpose Heterogeneous Catalysis under Mild Conditions
  作者：Santanu Chand、Shyam Chand Pal、Manas Mondal、Subrata Hota、Arun Pal、Rupam Sahoo、Madhab C. Das

  DOI：10.1021/acs.cgd.9b00823

  日期：2019.9.4

  In recent years, heterogeneous catalysis has become one of the most active domains in the research of metal–organic frameworks (MOFs). Here, two three-dimensional (3D) Co(II)-MOFs with open metal sites and exposed azo functionality on the MOF backbone have been constructed via mixed ligand assembly. Both the MOFs, 1 [Co2(1,4-NDC)2(L)(H2O)2(μ2-H2O)]·(DMF)2(H2O)}n and 2 [Co(fma)(L)(H2O)2]·S}n [1,4-NDC = 1,4-naphthalene dicarboxylic acid, fma = fumaric acid, L = 3,3′-azobis pyridine and S = disordered solvents] exhibit 3D frameworks with metal-bound aqua ligands. These metal-bound aqua ligands, as well as the lattice solvent molecules, could simply be removed upon activation affording the desolvated frameworks 1a and 2a respectively maintaining the original crystallinity with a varying number of open metal sites. Although crystallographic analysis revealed a porous structure for both the MOFs (34.4% and 14.3% void volume for 1 and 2, respectively), 1 showed a permanently microporous nature with a Brunauer–Emmett–Teller surface area of 197 m2 g–1 and moderate CO2 uptake capacity as established through a gas sorption study. Both MOFs exhibit efficient catalytic activity for the chemical fixation of CO2 to cyclic carbonate in the presence of a cocatalyst, cyanosilylation reaction, and Knoevenagel condensation under solvent-free and mild conditions and thus demonstrating their multipurpose heterogeneous catalytic nature. The limited pore space decorated with the exposed metal sites and the functional azo groups were efficient for size-selective heterogeneous catalysis with varying catalytic efficiencies. A systematic comparison in their catalytic performances could be made with the establishment of a structure–function relationship. Besides, both MOFs can easily be separated out from the reaction mixtures and reused for at least four cycles without any loss of catalytic activity and structural integrity.

  近年来，异相催化已成为金属-有机框架（MOFs）研究中最活跃的领域之一。在这里，通过混合配体组装构建了两个具有开放金属位点和在MOF骨架上暴露的偶氮功能的三维（3D）Co(II)-MOFs。两种MOFs，1 [Co2(1,4-NDC)2(L)(H2O)2(μ2-H2O)]·(DMF)2(H2O)}n 和 2 [Co(fma)(L)(H2O)2]·S}n [1,4-NDC = 1,4-萘二甲酸，fma = 富马酸，L = 3,3′-偶氮比啶，S = 无序溶剂] 展现了具有金属结合水配体的三维框架。这些金属结合水配体以及晶格溶剂分子可以在活化后简单去除，分别得到脱溶剂化框架1a和2a，同时保持了原有的结晶性，并具有不同数量的开放金属位点。尽管晶体学分析揭示了两个MOFs（1和2的孔隙体积分别为34.4%和14.3%）的多孔结构，但1表现出一种永久微孔特性，Brunauer–Emmett–Teller比表面积为197 m²/g，且通过气体吸附研究确定了适度的CO2吸附能力。这两种MOFs在存在协同催化剂的条件下，表现出高效的催化活性，能够将CO2固定化为环碳酸盐，进行氰基硅烷反应，以及在无溶剂和温和条件下进行Knoevenagel缩合，从而展示了其多功能的异相催化特性。有限的孔隙空间装饰着暴露的金属位点和功能性偶氮基团，使其在尺寸选择性异相催化中表现出不同的催化效率。通过建立结构-功能关系，可以对它们的催化性能进行系统的比较。此外，这两种MOFs可以轻松从反应混合物中分离出来，并在至少四个循环中重复使用，而不会损失催化活性和结构完整性。