(Z)-1-((tert-butyldiphenylsilyl)oxy)dec-5-en-4-ol | 1352034-77-5

• 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: (Z)-1-((tert-butyldiphenylsilyl)oxy)dec-5-en-4-ol
• 英文别名: (Z)-1-[tert-butyl(diphenyl)silyl]oxydec-5-en-4-ol
• CAS: 1352034-77-5
• 化学式: C₂₆H₃₈O₂Si
• 分子量: 410.672
• InChiKey: NKMRJMXNVSEZTO-YBEGLDIGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.45
• 重原子数：
  29
• 可旋转键数：
  12
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (Z)-1-iodohex-1-ene 、 4-((tert-butyldiphenylsilyl)oxy)butanal 在 锰 、 二氯二茂锆 、 C₃₅H₄₀Cl₅CrN₄NiO₆Si 、 lithium chloride 作用下， 以 乙二醇二甲醚 为溶剂， 反应 2.0h， 生成 (Z)-1-((tert-butyldiphenylsilyl)oxy)dec-5-en-4-ol 、 (E)-1-((tert-butyldiphenylsilyl)oxy)dec-5-en-4-ol
  参考文献：
  名称：

  Air-Stable Heterobimetallic Catalysts to Effect Ni/Cr-Mediated Couplings with a ca. 1:1 Molar Ratio of Coupling Partners at Low Catalyst Loadings

  摘要：

  Two air-stable NI,Cr-heterobimetallic catalysts have been prepared from ligands 7 and 11, obtained from scyllo-inositol in four and three steps, respectively. Both catalysts smoothly promote Ni/Cr-mediated coupling reactions with a ca. 1:1 molar ratio of coupling partners. The catalyst derived from 11 exhibits a better catalytic profile, thereby allowing Ni/Cr-mediated coupling reactions to be achieved with a wide range of substrates at a low catalyst loading in an operationally simple manner.

  DOI：

  10.1021/ol202878v

文献信息

• Selective Activation/Coupling of Polyhalogenated Nucleophiles in Ni/Cr-Mediated Reactions: Synthesis of C1–C19 Building Block of Halichondrin Bs
  作者：Wuming Yan、Zhanjie Li、Yoshito Kishi

  DOI：10.1021/jacs.5b03498

  日期：2015.5.20

  The C1-C19 building block 46 of halichondrin Bs was synthesized via a selective activation/coupling of beta-bromoenone 34 with aldehyde 35 in a Ni/Cr-mediated reaction. The first phase of study was a method development to effect a coupling of a naked vinylogous anion with an aldehyde. The study with the coupling of 9 + 10 -> 11 revealed: (1) beta-bromoenone 9b is a better nucleophile than the corresponding beta-iodo- and beta-chloroenones 9a,c; (2) (Me)(2)Phen(OMe)(2)center dot NiCl2 13b is a better Ni-catalyst than (Me)(2)Phen(H)(2)center dot NiCl2 13a; and (3) a low Ni-catalyst loading, for example, 0.05-0.1 mol % Ni-catalyst against 10 mol % Cr-catalyst, is crucial for an effective coupling. The second phase of study was a method development to realize a selective activation/coupling of polyhalogenated nucleophiles such as 34. The competition experiment of 10 + 9b over 10 + 31a-c revealed: (1) (Me)(2)Phen(OMe)(2)center dot NiCl2 13b is more effective than (Me)(2)Phen(H)(2)center dot NiCl2 13a for the required selective activation/coupling; (2) a low Ni-catalyst loading, for example, 0.05-0.1 mol % Ni-catalyst against 10 mol % Cr-catalyst, is crucial for discriminating beta-bromoenone 9b from the three types of vinyl iodides 31a-c. The third phase of study was an application of the developed method to execute the proposed coupling of 34 + 35 -> 36. For this application, a polyether-type Ni-catalyst 37c, readily soluble in the reaction medium, was introduced to achieve the selective activation/coupling with higher efficiency. With use of ion-exchange resin-based device, the coupling product 36 was transformed to the C1-C19 building block 46 of halichondrin Bs without purification/separation of the intermediates.