(E)-5-(tert-Butyl-dimethyl-silanyloxy)-3-(dimethyl-phenyl-silanyl)-pent-2-en-1-ol | 500591-02-6

• 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: (E)-5-(tert-Butyl-dimethyl-silanyloxy)-3-(dimethyl-phenyl-silanyl)-pent-2-en-1-ol
• 英文别名: (E)-5-[tert-butyl(dimethyl)silyl]oxy-3-[dimethyl(phenyl)silyl]pent-2-en-1-ol
• CAS: 500591-02-6
• 化学式: C₁₉H₃₄O₂Si₂
• 分子量: 350.649
• InChiKey: LFRKWDSBXNZVMZ-QGOAFFKASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.47
• 重原子数：
  23
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-5-(tert-Butyl-dimethyl-silanyloxy)-3-(dimethyl-phenyl-silanyl)-pent-2-en-1-ol 在 N,N-二甲基丙烯基脲 、 三乙胺 、 sodium iodide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 、 丙酮 为溶剂， 反应 0.25h， 生成 (1R,3S,8aR)-3-[tert-butyl(dimethyl)silyl]oxy-6-[(E)-5-[tert-butyl(dimethyl)silyl]oxy-3-[dimethyl(phenyl)silyl]pent-2-enyl]-8a-methyl-1-propan-2-yl-1,2,3,6,7,8-hexahydroazulen-5-one
  参考文献：
  名称：

  Formal Synthesis of (±)-Guanacastepene A

  摘要：

  A 17 step synthesis of 55, a late intermediate in Danishefsky's guanacastepene A synthesis, has been completed in 4% overall yield. Key features include the use of vinylmagnesium bromide in the Pd-catalyzed coupling with triflate 13 to give triene 16 without the formation of Heck products, a novel extension of the Stork-Jung vinylsilane Robinson annulation that provides tricyclic 2-hydroxymethylcyclohexenone 42 from 23b in four steps and 51% yield, the ability to obtain almost exclusively alpha'-alkylation of 35ba by the proper choice of protecting groups, and the ability to obtain the desired -alcohol selectively by reduction of keto alcohol 42 rather than keto ester 53.

  DOI：

  10.1021/jo026702j
• 作为产物：
  描述：

  dimethyl(phenyl)silyl lithium 、 5-[(tert-butyldimethylsilyl)oxy]pent-2-yn-1-ol 在 CuCN 作用下， 以 四氢呋喃 为溶剂， 以74%的产率得到(E)-5-(tert-Butyl-dimethyl-silanyloxy)-3-(dimethyl-phenyl-silanyl)-pent-2-en-1-ol
  参考文献：
  名称：

  Formal Synthesis of (±)-Guanacastepene A

  摘要：

  A 17 step synthesis of 55, a late intermediate in Danishefsky's guanacastepene A synthesis, has been completed in 4% overall yield. Key features include the use of vinylmagnesium bromide in the Pd-catalyzed coupling with triflate 13 to give triene 16 without the formation of Heck products, a novel extension of the Stork-Jung vinylsilane Robinson annulation that provides tricyclic 2-hydroxymethylcyclohexenone 42 from 23b in four steps and 51% yield, the ability to obtain almost exclusively alpha'-alkylation of 35ba by the proper choice of protecting groups, and the ability to obtain the desired -alcohol selectively by reduction of keto alcohol 42 rather than keto ester 53.

  DOI：

  10.1021/jo026702j

文献信息

• Formal Synthesis of (±)-Guanacastepene A
  作者：Bo Shi、Natalie A. Hawryluk、Barry B. Snider

  DOI：10.1021/jo026702j

  日期：2003.2.1

  A 17 step synthesis of 55, a late intermediate in Danishefsky's guanacastepene A synthesis, has been completed in 4% overall yield. Key features include the use of vinylmagnesium bromide in the Pd-catalyzed coupling with triflate 13 to give triene 16 without the formation of Heck products, a novel extension of the Stork-Jung vinylsilane Robinson annulation that provides tricyclic 2-hydroxymethylcyclohexenone 42 from 23b in four steps and 51% yield, the ability to obtain almost exclusively alpha'-alkylation of 35ba by the proper choice of protecting groups, and the ability to obtain the desired -alcohol selectively by reduction of keto alcohol 42 rather than keto ester 53.