(E)-(R)-4-(benzyloxy)-N-hydroxy-5,7-octadienamide | 154321-85-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (E)-(R)-4-(benzyloxy)-N-hydroxy-5,7-octadienamide
• 英文别名: (4R,5E)-N-hydroxy-4-phenylmethoxyocta-5,7-dienamide
• CAS: 154321-85-4
• 化学式: C₁₅H₁₉NO₃
• 分子量: 261.321
• InChiKey: HNHBGOOWMYVBLO-WMKWSGJFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  19
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  58.6
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-(R)-4-(benzyloxy)-N-hydroxy-5,7-octadienamide 在 palladium dichloride 咪唑 、 盐酸 、 sodium periodate 、 disodium hydrogenphosphate 、 sodium amalgam 、 四氧化锇 、 lithium aluminium tetrahydride 、 四溴化碳 、 氢气 、 4-甲基苯磺酸吡啶 、 N-甲基吗啉氧化物 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 乙腈 、 苯 为溶剂， 反应 45.5h， 生成 八倾吲嗪三醇
  参考文献：
  名称：

  New Chiral Route to (-)-Swainsonine via an Aqueous Acylnitroso Cycloaddition Approach

  摘要：

  A new noncarbohydrate-based enantioselective approach to (-)-swainsonine (1) is described, in which the aqueous intramolecular Diels-Alder reaction of a chiral acylnitroso diene has been employed as a key reaction. The intramolecular cycloaddition of the chiral hydroxamic acid 9, available from D-malic acid in 10 steps, with Pr4NIO4 was conducted under the conventional nonaqueous conditions using CHCl3 as a solvent, whereupon intermediacy acylnitroso compound 10 cyclized spontaneously to give the trans- and cis-1,2-oxazinolactams 11 and 12 with a low diastereoselction of 1.3:1 in 76 % combined yield. When the corresponding reaction was performed in water, it led to significant enhancements of trans selectivity of 4.1:1 as well as combined yield (89%). The trans adduct 11 was subjected to reductive N-O bond cleavage followed by diastereoselective hydroxylation with OsO4 to provide the 1,2-glycol 21, which was then converted to the amino alcohol 25. Intramolecular cyclodehydration of 25 with CBr4/PPhs/Et3N and subsequent deprotection furnished (-)-swainsonine (1).

  DOI：

  10.1021/jo00085a026
• 作为产物：
  描述：

  (2R,4R)-4-formyl-2-phenyl-1,3-dioxane 在 吡啶 、 氢氧化钾 、 sodium hydroxide 、 盐酸羟胺 、 potassium tert-butylate 、 碘 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二甲基亚砜 为溶剂， 反应 17.25h， 生成 (E)-(R)-4-(benzyloxy)-N-hydroxy-5,7-octadienamide
  参考文献：
  名称：

  New Chiral Route to (-)-Swainsonine via an Aqueous Acylnitroso Cycloaddition Approach

  摘要：

  A new noncarbohydrate-based enantioselective approach to (-)-swainsonine (1) is described, in which the aqueous intramolecular Diels-Alder reaction of a chiral acylnitroso diene has been employed as a key reaction. The intramolecular cycloaddition of the chiral hydroxamic acid 9, available from D-malic acid in 10 steps, with Pr4NIO4 was conducted under the conventional nonaqueous conditions using CHCl3 as a solvent, whereupon intermediacy acylnitroso compound 10 cyclized spontaneously to give the trans- and cis-1,2-oxazinolactams 11 and 12 with a low diastereoselction of 1.3:1 in 76 % combined yield. When the corresponding reaction was performed in water, it led to significant enhancements of trans selectivity of 4.1:1 as well as combined yield (89%). The trans adduct 11 was subjected to reductive N-O bond cleavage followed by diastereoselective hydroxylation with OsO4 to provide the 1,2-glycol 21, which was then converted to the amino alcohol 25. Intramolecular cyclodehydration of 25 with CBr4/PPhs/Et3N and subsequent deprotection furnished (-)-swainsonine (1).

  DOI：

  10.1021/jo00085a026

文献信息

• Enhanced stereoselectivity in aqueous intramolecular hetero Diels-Alder cycloaddition of chiral acylnitroso compounds
  作者：Masaichi Naruse、Sakae Aoyagi、Chihiro Kibayashi

  DOI：10.1016/s0040-4039(00)75847-3

  日期：1994.1

  In an aqueous medium, intramolecular hetero Diels-Alder cycloadditions of the chiral acylnitroso compounds, generated from the chiral hydroxamic acids by in situ periodate oxidation, shows a pronounced enhancement of the trans selectivity compared with the results obtained by employing nonaqueous conditions.

  在水介质中，通过手性高碘酸盐氧化从手性异羟肟酸生成的手性酰基亚硝基化合物的分子内杂Diels-Alder环加成反应，与采用非水条件得到的结果相比，显示出反式选择性的显着提高。