(1R,2R,4E,7S,10E,12E,14R,15S,16R)-2,15-bis(tert-butyldimethylsilyloxy)-7-((S)-4-(tert-butyldimethylsilyloxy)butan-2-yl)-10,12,14-trimethyl-8,17-dioxabicyclo[14.1.0]heptadeca-4,10,12-trien-9-one | 882491-73-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酯类和类似物
• 英文名称: (1R,2R,4E,7S,10E,12E,14R,15S,16R)-2,15-bis(tert-butyldimethylsilyloxy)-7-((S)-4-(tert-butyldimethylsilyloxy)butan-2-yl)-10,12,14-trimethyl-8,17-dioxabicyclo[14.1.0]heptadeca-4,10,12-trien-9-one
• 英文别名: (1R,2R,4E,7S,10E,12E,14R,15S,16R)-2,15-bis((tert-butyldimethylsilyl)oxy)-7-((2S)-4-((tert-butyldimethylsilyl)oxy)butan-2-yl)-10,12,14-trimethyl-8,17-dioxabicyclo[14.1.0]heptadeca-4,10,12-trien-9-one；(1R,2R,4E,7S,10E,12E,14R,15S,16R)-2,15-bis[[tert-butyl(dimethyl)silyl]oxy]-7-[(2S)-4-[tert-butyl(dimethyl)silyl]oxybutan-2-yl]-10,12,14-trimethyl-8,17-dioxabicyclo[14.1.0]heptadeca-4,10,12-trien-9-one
• CAS: 882491-73-8
• 化学式: C₄₀H₇₆O₆Si₃
• 分子量: 737.296
• InChiKey: PCKZIDGUTAJNOZ-OWKADAEESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.37
• 重原子数：
  49
• 可旋转键数：
  12
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  66.5
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (1R,2R,4E,7S,10E,12E,14R,15S,16R)-2,15-bis(tert-butyldimethylsilyloxy)-7-((S)-4-(tert-butyldimethylsilyloxy)butan-2-yl)-10,12,14-trimethyl-8,17-dioxabicyclo[14.1.0]heptadeca-4,10,12-trien-9-one 在 fluorosilic acid 、 4-甲基苯磺酸吡啶 、 双(三甲基硅烷基)氨基钾 、 碳酸氢钠 、 戴斯-马丁氧化剂 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 乙腈 为溶剂， 反应 90.33h， 生成 FD-891
  参考文献：
  名称：

  Enantioselective Total Synthesis of FD-891

  摘要：

  The enantioselective synthesis of FD-891 has been achieved with a longest linear sequence of 21 steps. The synthetic strategy involves the use of aldol additions of a chlorotitanium enolate of N-acylthiazolidinethiones as the key reaction to establish 6 of the 10 stereogenic centers. A key cross-metathesis and a late-stage Julia olefination serve to assemble three key subunits.

  DOI：

  10.1021/ja060018v
• 作为产物：
  描述：

  (2E,4E,6R,7S)-ethyl 7-(tert-butyldimethylsilyloxy)-7-((2R,3S)-3-((R)-1-hydroxybut-3-enyl)oxiran-2-yl)-2,4,6-trimethylhepta-2,4-dienoate 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 2,6-二甲基吡啶 、 potassium tert-butyldimethylsilanolate 、 2,4,6-三氯苯甲酰氯 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 60.0h， 生成 (1R,2R,4E,7S,10E,12E,14R,15S,16R)-2,15-bis(tert-butyldimethylsilyloxy)-7-((S)-4-(tert-butyldimethylsilyloxy)butan-2-yl)-10,12,14-trimethyl-8,17-dioxabicyclo[14.1.0]heptadeca-4,10,12-trien-9-one
  参考文献：
  名称：

  Stereoselective Total Synthesis of FD-891

  摘要：

  FD-891, a structurally unique 16-membered macrolide having anticancer activity, was synthesized according to a strategy employing asymmetric allylation, Prins cyclization, cross-metathesis reaction, Yamaguchi lactonization, and Julia-Kocienski olefination.

  DOI：

  10.1021/jo302205t

文献信息

• A Concise and Unified Strategy for Synthesis of the C1–C18 Macrolactone Fragments of FD-891, FD-892 and Their Analogues: Formal Total Synthesis of FD-891
  作者：Naoki Kanoh、Ayano Kawamata、Tomohiro Itagaki、Yuta Miyazaki、Kenzo Yahata、Eunsang Kwon、Yoshiharu Iwabuchi

  DOI：10.1021/ol502633j

  日期：2014.10.3

  A concise and unified strategy for the synthesis of C1–C18 macrolactone fragments of FD-891 and FD-892 as well as their analogues is reported. The strategy includes a stereoselective vinylogous Mukaiyama aldol reaction (VMAR) using chiral silyl ketene N,O-acetal to construct C6–C7 stereocenters, an E-selective ring closing metathesis to construct a C12–C13 olefin, and stereodivergent construction of

  报道了一种简明统一的合成策略，用于合成FD-891和FD-892及其类似物的C1-C18大内酯片段。该策略包括使用手性甲硅烷基乙烯酮N，O-缩醛构建C6–C7立体中心的立体选择性乙烯类Mukaiyama醛醇缩醛反应（VMAR），构建C12–C13烯烃的E选择环闭合复分解反应以及C8–C3的立体发散结构C9环氧化物。
• Enantioselective Total Synthesis of FD-891
  作者：Michael T. Crimmins、Franck Caussanel

  DOI：10.1021/ja060018v

  日期：2006.3.1

  The enantioselective synthesis of FD-891 has been achieved with a longest linear sequence of 21 steps. The synthetic strategy involves the use of aldol additions of a chlorotitanium enolate of N-acylthiazolidinethiones as the key reaction to establish 6 of the 10 stereogenic centers. A key cross-metathesis and a late-stage Julia olefination serve to assemble three key subunits.
• Stereoselective Total Synthesis of FD-891
  作者：J. S. Yadav、Sukant Kishore Das、G. Sabitha

  DOI：10.1021/jo302205t

  日期：2012.12.21

  FD-891, a structurally unique 16-membered macrolide having anticancer activity, was synthesized according to a strategy employing asymmetric allylation, Prins cyclization, cross-metathesis reaction, Yamaguchi lactonization, and Julia-Kocienski olefination.