(R)-6-((E,3R,4R,5R)-8-(benzyldimethylsilyl)-3-trimethylsiloxy-4-hydroxy-6-tert-butyldimethylsiloxybut-3-methyloct-1-en-7-ynyl)-5,6-dihydropyran-2-one | 850146-95-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: (R)-6-((E,3R,4R,5R)-8-(benzyldimethylsilyl)-3-trimethylsiloxy-4-hydroxy-6-tert-butyldimethylsiloxybut-3-methyloct-1-en-7-ynyl)-5,6-dihydropyran-2-one
• 英文别名: (2R)-2-[(E,3R,4R,6R)-8-[benzyl(dimethyl)silyl]-6-[tert-butyl(dimethyl)silyl]oxy-4-hydroxy-3-methyl-3-triethylsilyloxyoct-1-en-7-ynyl]-2,3-dihydropyran-6-one
• CAS: 850146-95-1
• 化学式: C₃₅H₅₈O₅Si₃
• 分子量: 643.099
• InChiKey: BNTULWHBLFEEAB-XDWRIDHVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.37
• 重原子数：
  43
• 可旋转键数：
  16
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  65
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (R)-6-((E,3R,4R,5R)-8-(benzyldimethylsilyl)-3-trimethylsiloxy-4-hydroxy-6-tert-butyldimethylsiloxybut-3-methyloct-1-en-7-ynyl)-5,6-dihydropyran-2-one 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 2,4,6-三异丙基苯磺酰基肼 、 四丁基氟化铵 、 碳酸氢钠 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 18.5h， 生成 5,6-二氢-6-(3,4,6,13-四羟基-3-甲基-1,7,9,11-十三碳四烯基)-2H-吡喃-2-酮
  参考文献：
  名称：

  Dinuclear Asymmetric Zn Aldol Additions:  Formal Asymmetric Synthesis of Fostriecin

  摘要：

  Direct asymmetric aldol reactions constitute a powerful methodology for the efficient synthesis of complex natural products. Herein we report the first application of our recently reported dinuclear Zn-catalyzed direct aldol addition of alkynyl ketones to aldehydes in a short and efficient formal asymmetric synthesis of fostriecin, a potent cyctotoxic natural product. This work highlights not only the power of the aldol methodology but also the utility of the akynyl silane aldol adducts, as it is subsequently utilized in a vinyl silane cross-coupling reaction which affords the target molecule in 14 steps for the longest linear sequence in 8.5% overall yield.

  DOI：

  10.1021/ja042435i
• 作为产物：
  描述：

  triethyl-[(1E,3R)-1-iodohexa-1,5-dien-3-yl]oxysilane 在 Grubbs catalyst first generation 、 N-乙基二丙胺 、 氢氟酸 、 水 、 N,N-二异丙基乙胺 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 烯丙基溴化镁 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 乙腈 为溶剂， 反应 31.58h， 生成 (R)-6-((E,3R,4R,5R)-8-(benzyldimethylsilyl)-3-trimethylsiloxy-4-hydroxy-6-tert-butyldimethylsiloxybut-3-methyloct-1-en-7-ynyl)-5,6-dihydropyran-2-one
  参考文献：
  名称：

  Dinuclear Asymmetric Zn Aldol Additions:  Formal Asymmetric Synthesis of Fostriecin

  摘要：

  Direct asymmetric aldol reactions constitute a powerful methodology for the efficient synthesis of complex natural products. Herein we report the first application of our recently reported dinuclear Zn-catalyzed direct aldol addition of alkynyl ketones to aldehydes in a short and efficient formal asymmetric synthesis of fostriecin, a potent cyctotoxic natural product. This work highlights not only the power of the aldol methodology but also the utility of the akynyl silane aldol adducts, as it is subsequently utilized in a vinyl silane cross-coupling reaction which affords the target molecule in 14 steps for the longest linear sequence in 8.5% overall yield.

  DOI：

  10.1021/ja042435i

文献信息

• Synthesis of Dehydro-Dephospho-Fostriecin and Formal Total Synthesis of Fostriecin
  作者：Dong Gao、Bohui Li、George A. O’Doherty

  DOI：10.1021/acs.orglett.9b03120

  日期：2019.10.18

  A formal synthesis of fostriecin (1) and a total synthesis of its related congener dihydro-dephospho-fostriecin 2 have been achieved. The route relies upon the use of the Sharpless dihydroxylation to set the absolute stereochemistry at C-8/9 and Noyori transfer hydrogenation and Leighton allylation to set the C-11 and C-5 relative stereochemistry, respectively. Finally, the divergent functionalization

  已经成功合成了合成的邻苯二酚（1）及其相关的同类物二氢-去磷酸-磷霉素2。该路线依赖于使用Sharpless二羟基化将绝对立体化学设定在C -8/9和Noyori转移氢化和Leighton烯丙基化分别设定C -11和C -5相对立体化学。最后，一个的发散官能Ç -12/13炔被用来建立Z，E脱氢脱磷酸fostriecin的-dienyne 2和Z，Z，E fostriecin（的三烯1）。