(2R,3R,4R,5S)-4-Formyl-2,3-(isopropylidenedioxy)-5-<(1R)-1,2-(isopropylidenedioxy)ethyl>-4-<4-(tert-butyldimethylsilyloxy)butyl>tetrahydrofuran | 152492-06-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,3R,4R,5S)-4-Formyl-2,3-(isopropylidenedioxy)-5-<(1R)-1,2-(isopropylidenedioxy)ethyl>-4-<4-(tert-butyldimethylsilyloxy)butyl>tetrahydrofuran
• 英文别名: (3aR,5S,6R,6aR)-6-[4-[tert-butyl(dimethyl)silyl]oxybutyl]-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-5,6a-dihydro-3aH-furo[2,3-d][1,3]dioxole-6-carbaldehyde
• CAS: 152492-06-3
• 化学式: C₂₃H₄₂O₇Si
• 分子量: 458.668
• InChiKey: GEMSTWKEYKLXQQ-BYXWFHEMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.39
• 重原子数：
  31
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.96
• 拓扑面积：
  72.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (2R,3R,4R,5S)-4-Formyl-2,3-(isopropylidenedioxy)-5-<(1R)-1,2-(isopropylidenedioxy)ethyl>-4-<4-(tert-butyldimethylsilyloxy)butyl>tetrahydrofuran 在 盐酸 、 六甲基磷酰三胺 、 sodium tetrahydroborate 、 sodium periodate 、 molecular sieve 、 samarium diiodide 、 18-冠醚-6 、 Raney nickel T-4 、 四丁基氟化铵 、 双(三甲基硅烷基)氨基钾 、 sodium hydride 、 异丙醇 、 pyridinium chlorochromate 、 三氟乙酸 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 213.5h， 生成 (3aS,4R,7aR)-4-Methyl-4-vinylhexahydrobenzofuran-2(3H)-one
  参考文献：
  名称：

  Total syntheses of (-)-anastrephin, (-)-epianastrephin, and their 7a-epimers: use of samarium(II) iodide-mediated intramolecular reductive coupling for the construction of their hexahydrobenzofuran-2(3H)-one skeletons

  摘要：

  D-Glucose-derived alpha,beta-unsaturated ester 17, which includes a geminally and differntially substituted gamma-carbon and a terminal aldehyde functionality, was subjected to a SMI2-Mediated intramolecular reductive coupling reaction in a THF solution containing 1/10 volume of HMPA. The reaction proceeded with moderate stereoselectivity to provide a diastereomeric mixture of hexahydrobenzofuran-2 (3H)-ones, in which cis-fused product 25 was obtained as the major isomer in 35% isolated yield. Two trans-fused coupling products 26 (17%) and 27 (14%) were also obtained. Starting from major product 25, the insect sex attractants (-)-anastrephin (1) and (-)-epianastrephin (2) were synthesized enantiospecifically. Two unnatural stereocongeners, (-)-7a-epi-anastrephin (3) and (-)-7a-epi-epianastrephin (4), were also derived from 25.

  DOI：

  10.1021/jo00075a021
• 作为产物：
  描述：

  (2R,3R,4R,5S)-4-(2-hydroxyethyl)-2,3-(isopropylidenedioxy)-5-<(1R)-1,2-(isopropylidenedioxy)ethyl>-4-vinyltetrahydrofuran 在 咪唑 、 lithium aluminium tetrahydride 、 sodium hydride 、 臭氧 、 三苯基膦 、 sodium chloride 、 偶氮二甲酸二乙酯 、 碘甲烷 作用下， 以 四氢呋喃 、 水 、 二甲基亚砜 、 N,N-二甲基甲酰胺 为溶剂， 生成 (2R,3R,4R,5S)-4-Formyl-2,3-(isopropylidenedioxy)-5-<(1R)-1,2-(isopropylidenedioxy)ethyl>-4-<4-(tert-butyldimethylsilyloxy)butyl>tetrahydrofuran
  参考文献：
  名称：

  mar（II）碘化物介导的还原环化方法可完全合成昆虫性引诱剂（-）-阿斯特拉芬

  摘要：

  在THF-HMPA中使用SmI 2有效地实现了对映体纯的γ，γ-差异C-取代的α，β-不饱和酯5的分子内还原环化，该酯具有末端醛官能团。从主要的环化产物6开始，（-）-anastrephin的对映体特异性全合成。1完成。

  DOI：

  10.1016/s0040-4039(00)74773-3

文献信息

• Samarium(II) iodide-mediated reductive cyclization approach to total synthesis of the insect sex Attractant (−)-anastrephin
  作者：Kin-ichi Tadano、Yoshiaki Isshiki、Masaki Minami、Seiichiro Ogawa

  DOI：10.1016/s0040-4039(00)74773-3

  日期：1992.12

  C-substituted α,β-unsaturated ester 5 having a terminal aldehyde functionality, was effectively achieved using SmI2 in THF-HMPA. Starting with the major cyclization product 6, enantiospecific total synthesis of (−)-anastrephin. 1 was completed.

  在THF-HMPA中使用SmI 2有效地实现了对映体纯的γ，γ-差异C-取代的α，β-不饱和酯5的分子内还原环化，该酯具有末端醛官能团。从主要的环化产物6开始，（-）-anastrephin的对映体特异性全合成。1完成。
• Total syntheses of (-)-anastrephin, (-)-epianastrephin, and their 7a-epimers: use of samarium(II) iodide-mediated intramolecular reductive coupling for the construction of their hexahydrobenzofuran-2(3H)-one skeletons
  作者：Kinichi Tadano、Yoshiaki Isshiki、Masaki Minami、Seiichiro Ogawa

  DOI：10.1021/jo00075a021

  日期：1993.11

  D-Glucose-derived alpha,beta-unsaturated ester 17, which includes a geminally and differntially substituted gamma-carbon and a terminal aldehyde functionality, was subjected to a SMI2-Mediated intramolecular reductive coupling reaction in a THF solution containing 1/10 volume of HMPA. The reaction proceeded with moderate stereoselectivity to provide a diastereomeric mixture of hexahydrobenzofuran-2 (3H)-ones, in which cis-fused product 25 was obtained as the major isomer in 35% isolated yield. Two trans-fused coupling products 26 (17%) and 27 (14%) were also obtained. Starting from major product 25, the insect sex attractants (-)-anastrephin (1) and (-)-epianastrephin (2) were synthesized enantiospecifically. Two unnatural stereocongeners, (-)-7a-epi-anastrephin (3) and (-)-7a-epi-epianastrephin (4), were also derived from 25.