(R)-1-(tert-butyldiphenylsilyloxy)-7-octen-4-ol | 169304-50-1

• 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: (R)-1-(tert-butyldiphenylsilyloxy)-7-octen-4-ol
• 英文别名: (R)-1-tert-Butyldiphenylsilyloxyoct-7-en-4-ol；(4R)-1-[tert-butyl(diphenyl)silyl]oxyoct-7-en-4-ol
• CAS: 169304-50-1
• 化学式: C₂₄H₃₄O₂Si
• 分子量: 382.618
• InChiKey: YEDHPKNWMOCXJI-OAQYLSRUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.67
• 重原子数：
  27
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 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：

  (R)-1-(tert-butyldiphenylsilyloxy)-7-octen-4-ol 在 sodium tetrahydroborate 、 偶氮二甲酸二异丙酯 、 四丁基氟化铵 、 甲基磺酰氯 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 28.0h， 生成 (S)-3-(1-Hydroxyoct-7-en-4-yl)-2,3-dihydrooxazol-2-one
  参考文献：
  名称：

  Diastereoselective synthesis of 2,5-disubstituted 3-hydroxypyrrolidine and 2,6-disubstituted 3-hydroxypiperidine derivatives by radical cyclisation; synthesis of (+)-bulgecinine and (–)-desoxoprosopinine

  摘要：

  Cyclisation of the O-stannyl ketyl, generated from the aldehyde 17 by reaction with tributyltin hydride in the presence of AIBN, gives the 5-benzyloxymethyl-7-hydroxypyrrolooxazolidin as a diastereoisomeric mixture of 7 alpha-ol 18 and 7 beta-ol 19 (2: 1), with high diastereoselectivity with respect to the 5,7a positions, (+)-Bulgecinine 8 is enantioselectively synthesised by stereospecific reduction of the ketone 20, derived from compounds 18 and 19. In a similar way, cyclisation of compound 40 gives a 2: 1 mixture of compounds 41 and 42. Conversion of compound 41 into (-)-desoxoprosopinine 9 is successfully achieved.

  DOI：

  10.1039/p19960000793
• 作为产物：
  描述：

  3-[(4S)-2,2-二甲基-1,3-二氧戊烷-4-基]-丙醇 在 吡啶 、 咪唑 、 2,4,6-三甲基苯磺酰氯 、 copper(l) iodide 、 18-冠醚-6 、 sodium hydride 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 生成 (R)-1-(tert-butyldiphenylsilyloxy)-7-octen-4-ol
  参考文献：
  名称：

  Enantioselective Synthesis of (−)-desoxoprosopinine by radical cyclization

  摘要：

  Reaction of the aldehyde 12 with tributyltin hydride in the presence of AIBN gave a mixture of 13 as a 2:1 mixture of 8 beta-ol. and 8 alpha-ol. Conversion of 14, derived from 13, to (-)-desoxoprosopinine 3 was successfully achieved.

  DOI：

  10.1016/0957-4166(95)00189-v

文献信息

• Formal Total Synthesis of Amphidinolide E
  作者：Lluís Bosch、Laura Mola、Elena Petit、Mar Saladrigas、Jorge Esteban、Anna M. Costa、Jaume Vilarrasa

  DOI：10.1021/acs.joc.7b01973

  日期：2017.10.20

  A formal total synthesis of the cytotoxic macrolide amphidinolide E is reported. The strategic steps are three Julia–Kocienski reactions (J–K), for the formation of the C5–C6, C9–C10, and C17–C18 double bonds, a Suzuki–Molander C21–C22 bond formation reaction, and a Kita–Trost macrolactonization. The “instability” of the two dienic systems and of the stereocenter at C2 (allylic methine, α to the carboxy

  据报道，细胞毒性大环内酯类两性霉素E的正式全合成。战略步骤是三个Julia–Kocienski反应（J–K），用于形成C5–C6，C9–C10和C17–C18双键，Suzuki-Molander C21–C22键形成反应以及Kita– Trost大内酯化。两个二烯系和C2（烯丙基次甲基，α到羧基的α）的立体中心和C17-OH和C18-OH的保护基的“不稳定性”提出了艰巨的挑战。每个Julia-Kocienski烯烃的聚合反应均经过系统优化，以提供最高的E / Z比。
• Enantioselective Synthesis of (−)-desoxoprosopinine by radical cyclization
  作者：Yoko Yuasa、Jun Ando、Shiroshi Shibuya

  DOI：10.1016/0957-4166(95)00189-v

  日期：1995.7

  Reaction of the aldehyde 12 with tributyltin hydride in the presence of AIBN gave a mixture of 13 as a 2:1 mixture of 8 beta-ol. and 8 alpha-ol. Conversion of 14, derived from 13, to (-)-desoxoprosopinine 3 was successfully achieved.
• Diastereoselective synthesis of 2,5-disubstituted 3-hydroxypyrrolidine and 2,6-disubstituted 3-hydroxypiperidine derivatives by radical cyclisation; synthesis of (+)-bulgecinine and (–)-desoxoprosopinine
  作者：Yoko Yuasa、Jun Ando、Shiroshi Shibuya

  DOI：10.1039/p19960000793

  日期：——

  Cyclisation of the O-stannyl ketyl, generated from the aldehyde 17 by reaction with tributyltin hydride in the presence of AIBN, gives the 5-benzyloxymethyl-7-hydroxypyrrolooxazolidin as a diastereoisomeric mixture of 7 alpha-ol 18 and 7 beta-ol 19 (2: 1), with high diastereoselectivity with respect to the 5,7a positions, (+)-Bulgecinine 8 is enantioselectively synthesised by stereospecific reduction of the ketone 20, derived from compounds 18 and 19. In a similar way, cyclisation of compound 40 gives a 2: 1 mixture of compounds 41 and 42. Conversion of compound 41 into (-)-desoxoprosopinine 9 is successfully achieved.