(2S)-4-(benzenesulfonyl)-1-[(2S,3S,5R)-5-[[tert-butyl(diphenyl)silyl]oxymethyl]-3-triethylsilyloxyoxolan-2-yl]-5-[(2S,6S)-6-methoxy-2-[(E)-5-tri(propan-2-yl)silyloxypent-1-enyl]-2,5-dihydropyran-6-yl]-2-methylpentan-3-one | 948297-30-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2S)-4-(benzenesulfonyl)-1-[(2S,3S,5R)-5-[[tert-butyl(diphenyl)silyl]oxymethyl]-3-triethylsilyloxyoxolan-2-yl]-5-[(2S,6S)-6-methoxy-2-[(E)-5-tri(propan-2-yl)silyloxypent-1-enyl]-2,5-dihydropyran-6-yl]-2-methylpentan-3-one
• CAS: 948297-30-1
• 化学式: C₅₉H₉₂O₉SSi₃
• 分子量: 1061.7
• InChiKey: LJTCWZLGTKOWPM-WTUVKKNISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.16
• 重原子数：
  72
• 可旋转键数：
  29
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  115
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  (2S)-4-(benzenesulfonyl)-1-[(2S,3S,5R)-5-[[tert-butyl(diphenyl)silyl]oxymethyl]-3-triethylsilyloxyoxolan-2-yl]-5-[(2S,6S)-6-methoxy-2-[(E)-5-tri(propan-2-yl)silyloxypent-1-enyl]-2,5-dihydropyran-6-yl]-2-methylpentan-3-one 在 sodium dihydrogenphosphate 、 sodium-mercury amalgam (5%) 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 1.0h， 以92%的产率得到(2S)-1-[(2S,3S,5R)-5-[[tert-butyl(diphenyl)silyl]oxymethyl]-3-triethylsilyloxyoxolan-2-yl]-5-[(2S,6R)-6-methoxy-2-[(E)-5-tri(propan-2-yl)silyloxypent-1-enyl]-2,5-dihydropyran-6-yl]-2-methylpentan-3-one
  参考文献：
  名称：

  Total Synthesis of (+)-Azaspiracid-1. An Exhibition of the Intricacies of Complex Molecule Synthesis

  摘要：

  The synthesis of the marine neurotoxin azaspiracid-1 has been accomplished. The individual fragments were synthesized by catalytic enantioselective processes: A hetero-Diels-Alder reaction to afford the E- and HI-ring fragments, a carbonyl-ene reaction to furnish the CD-ring fragment, and a Mukaiyama aldol reaction to deliver the FG-ring fragment. The subsequent fragment couplings were accomplished by aldol and sulfone anion methodologies. All ketalization events to form the nonacyclic target were accomplished under equilibrating conditions utilizing the imbedded configurations of the molecule to adopt one favored conformation. A final fragment coupling of the anomeric EFGHI-sulfone anion to the ABCD-aldehyde completed the convergent synthesis of (+)-azaspiracid-1.

  DOI：

  10.1021/ja804659n
• 作为产物：
  描述：

  3-tert-butyldiphenylsilyloxy-2-methylpropene 在 2,2-di(S-4-tBu-4,5-dihydrooxazol-2-yl)propane Cu(II) complex 吡啶 、 咪唑 、 三乙基硅烷 、 pyridine-SO3 complex 、 三氟化硼乙醚 、 三甲基铝 、 叔丁基锂 、 4-甲基苯磺酸吡啶 、 L-Selectride 、 sodium hydride 、 LiDBB 、 戴斯-马丁氧化剂 、 臭氧 、 二甲基亚砜 、 N,N-二异丙基乙胺 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 12.0h， 生成 (2S)-4-(benzenesulfonyl)-1-[(2S,3S,5R)-5-[[tert-butyl(diphenyl)silyl]oxymethyl]-3-triethylsilyloxyoxolan-2-yl]-5-[(2S,6S)-6-methoxy-2-[(E)-5-tri(propan-2-yl)silyloxypent-1-enyl]-2,5-dihydropyran-6-yl]-2-methylpentan-3-one
  参考文献：
  名称：

  （+）-氮杂螺旋酸-1的全合成。第一部分：完全精制的ABCD醛的合成。

  摘要：

  DOI：

  10.1002/anie.200701515

文献信息

• Total Synthesis of (+)-Azaspiracid-1. An Exhibition of the Intricacies of Complex Molecule Synthesis
  作者：David A. Evans、Lisbet Kværnø、Travis B. Dunn、André Beauchemin、Brian Raymer、Jason A. Mulder、Edward J. Olhava、Martin Juhl、Katsuji Kagechika、David A. Favor

  DOI：10.1021/ja804659n

  日期：2008.12.3

  The synthesis of the marine neurotoxin azaspiracid-1 has been accomplished. The individual fragments were synthesized by catalytic enantioselective processes: A hetero-Diels-Alder reaction to afford the E- and HI-ring fragments, a carbonyl-ene reaction to furnish the CD-ring fragment, and a Mukaiyama aldol reaction to deliver the FG-ring fragment. The subsequent fragment couplings were accomplished by aldol and sulfone anion methodologies. All ketalization events to form the nonacyclic target were accomplished under equilibrating conditions utilizing the imbedded configurations of the molecule to adopt one favored conformation. A final fragment coupling of the anomeric EFGHI-sulfone anion to the ABCD-aldehyde completed the convergent synthesis of (+)-azaspiracid-1.
• Total Synthesis of (+)-Azaspiracid-1. Part I: Synthesis of the Fully Elaborated ABCD Aldehyde
  作者：David A. Evans、Lisbet Kværnø、Jason A. Mulder、Brian Raymer、Travis B. Dunn、André Beauchemin、Edward J. Olhava、Martin Juhl、Katsuji Kagechika

  DOI：10.1002/anie.200701515

  日期：2007.6.18