(2R,3R)-3-(benzyloxy)-2-<(1S,2R)-3-hydroxy-1,2-(isopropylidenedioxy)propyl>piperidine | 154815-11-9

• 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: (2R,3R)-3-(benzyloxy)-2-<(1S,2R)-3-hydroxy-1,2-(isopropylidenedioxy)propyl>piperidine
• 英文别名: (2R,3R)-3-(benzyloxy)-2-[(1S,2R)-3-hydroxy-1,2-(isopropylidenedioxy)propyl]piperidine；[(4R,5S)-2,2-dimethyl-5-[(2R,3R)-3-phenylmethoxypiperidin-2-yl]-1,3-dioxolan-4-yl]methanol
• CAS: 154815-11-9
• 化学式: C₁₈H₂₇NO₄
• 分子量: 321.417
• InChiKey: IGGPBWHGMJRTRR-QBPKDAKJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  60
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2R,3R)-3-(benzyloxy)-2-<(1S,2R)-3-hydroxy-1,2-(isopropylidenedioxy)propyl>piperidine 在 palladium dichloride 盐酸 、 四溴化碳 、 氢气 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 15.33h， 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 、 咪唑 、 氢氧化钾 、 sodium hydroxide 、 sodium periodate 、 disodium hydrogenphosphate 、 sodium amalgam 、 四氧化锇 、 lithium aluminium tetrahydride 、 盐酸羟胺 、 potassium tert-butylate 、 碘 、 4-甲基苯磺酸吡啶 、 二异丁基氢化铝 、 N-甲基吗啉氧化物 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 乙醇 、 水 、 二甲基亚砜 、 N,N-二甲基甲酰胺 、 乙腈 、 苯 为溶剂， 反应 47.42h， 生成 (2R,3R)-3-(benzyloxy)-2-<(1S,2R)-3-hydroxy-1,2-(isopropylidenedioxy)propyl>piperidine
  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

• New Chiral Route to (-)-Swainsonine via an Aqueous Acylnitroso Cycloaddition Approach
  作者：Masaichi Naruse、Sakae Aoyagi、Chihiro Kibayashi

  DOI：10.1021/jo00085a026

  日期：1994.3

  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).