(R)-6-[(1E,7Z)-(3R,4R,6R)-8-(Benzyl-dimethyl-silanyl)-6-(tert-butyl-dimethyl-silanyloxy)-4-hydroxy-3-methyl-3-triethylsilanyloxy-octa-1,7-dienyl]-5,6-dihydro-pyran-2-one | 850146-96-2

• 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-[(1E,7Z)-(3R,4R,6R)-8-(Benzyl-dimethyl-silanyl)-6-(tert-butyl-dimethyl-silanyloxy)-4-hydroxy-3-methyl-3-triethylsilanyloxy-octa-1,7-dienyl]-5,6-dihydro-pyran-2-one
• 英文别名: (2R)-2-[(1E,3R,4R,6R,7Z)-8-[benzyl(dimethyl)silyl]-6-[tert-butyl(dimethyl)silyl]oxy-4-hydroxy-3-methyl-3-triethylsilyloxyocta-1,7-dienyl]-2,3-dihydropyran-6-one
• CAS: 850146-96-2
• 化学式: C₃₅H₆₀O₅Si₃
• 分子量: 645.115
• InChiKey: QGSZBPBXMISYKH-KLTJCWIDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.92
• 重原子数：
  43
• 可旋转键数：
  17
• 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：

  (2E,4Z)-5-iodopenta-2,4-dien-1-ol 、 (R)-6-[(1E,7Z)-(3R,4R,6R)-8-(Benzyl-dimethyl-silanyl)-6-(tert-butyl-dimethyl-silanyloxy)-4-hydroxy-3-methyl-3-triethylsilanyloxy-octa-1,7-dienyl]-5,6-dihydro-pyran-2-one 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 6.5h， 以54%的产率得到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：

  苄基二甲基氯硅烷 在 咪唑 、 Grubbs catalyst first generation 、 正丁基锂 、 N-乙基二丙胺 、 4 A molecular sieve 、 chiral Ru catalyst 、 2,4,6-三异丙基苯磺酰基肼 、 camphor-10-sulfonic acid 、 氢氟酸 、 水 、 diethylzinc 、 碳酸氢钠 、 N,N-二异丙基乙胺 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 (S,S)-(+)-2,6-双[2-(羟基二苯甲基)-1-吡咯烷基-甲基]-4-甲基苯酚 、 烯丙基溴化镁 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 异丙醇 、 丙酮 、 乙腈 为溶剂， 反应 130.75h， 生成 (R)-6-[(1E,7Z)-(3R,4R,6R)-8-(Benzyl-dimethyl-silanyl)-6-(tert-butyl-dimethyl-silanyloxy)-4-hydroxy-3-methyl-3-triethylsilanyloxy-octa-1,7-dienyl]-5,6-dihydro-pyran-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

• Dinuclear Asymmetric Zn Aldol Additions:  Formal Asymmetric Synthesis of Fostriecin
  作者：Barry M. Trost、Mathias U. Frederiksen、Julien P. N. Papillon、Paul E. Harrington、Seunghoon Shin、Brock T. Shireman

  DOI：10.1021/ja042435i

  日期：2005.3.1

  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.