tert-butyl (2R,3S,4S,5R,αR)-2-hydroxy-3-[N-but-3'-enyl-N-(α-methyl-p-methoxybenzyl)amino]-4,5-O-isopropylidenehept-6-enoate | 1273232-31-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: tert-butyl (2R,3S,4S,5R,αR)-2-hydroxy-3-[N-but-3'-enyl-N-(α-methyl-p-methoxybenzyl)amino]-4,5-O-isopropylidenehept-6-enoate
• 英文别名: tert-butyl (2R,3S)-3-[but-3-enyl-[(1R)-1-(4-methoxyphenyl)ethyl]amino]-3-[(4S,5R)-5-ethenyl-2,2-dimethyl-1,3-dioxolan-4-yl]-2-hydroxypropanoate
• CAS: 1273232-31-7
• 化学式: C₂₇H₄₁NO₆
• 分子量: 475.626
• InChiKey: ZRUXGCUUQFJWEL-REXJZNOJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  34
• 可旋转键数：
  13
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  77.5
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  tert-butyl (2R,3S,4S,5R,αR)-2-hydroxy-3-[N-but-3'-enyl-N-(α-methyl-p-methoxybenzyl)amino]-4,5-O-isopropylidenehept-6-enoate 在 Grubbs catalyst first generation 、 盐酸 、 sodium periodate 、 lithium aluminium tetrahydride 、 碘 、 碳酸氢钠 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 46.0h， 生成 (1R,2S,3S,7aR)-1,2-dihydroxy-3-hydroxymethylhexahydro-1H-pyrrolizidine
  参考文献：
  名称：

  Asymmetric Synthesis of Polyhydroxylated Pyrrolizidines via Transannular Iodoamination with Concomitant N-Debenzylation

  摘要：

  The doubly diastereoselective "matched" conjugate addition of lithium (R)-N-but-3-enyl-N-(alpha-methyl-p-methoxybenzyl)amide to tert-butyl (4S,5R,E)-4,5-O-isopropylidene-2,7-dienoate (derived from D-ribose in 3 steps) and in situ enolate oxidation with (-)-camphorsulfonyloxaziridine was followed by ring-closing metathesis with Grubbs 1 to give a hexahydroazocine scaffold. Subsequent treatment with I-2 resulted in transannular Iodoamination accompanied by loss of the alpha-methyl-p-methoxybenzyl group to give the corresponding pyrrolizidine scaffold as a single diastereoisomer upon direct crystallization from the crude reaction mixture. Further functional group manipulations enabled the preparation of (-)-7a-epi-hyacinthacine A1.

  DOI：

  10.1021/ol103090z
• 作为产物：
  描述：

  (R)-(+)-1-(4-甲氧基苯)乙胺 在 正丁基锂 、 potassium carbonate 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 12.0h， 生成 tert-butyl (3S,4S,5R,αR)-3-[N-but-3'-enyl-N-(α-methyl-p-methoxybenzyl)amino]-4,5-O-isopropylidenehept-6-enoate 、 tert-butyl (2R,3S,4S,5R,αR)-2-hydroxy-3-[N-but-3'-enyl-N-(α-methyl-p-methoxybenzyl)amino]-4,5-O-isopropylidenehept-6-enoate
  参考文献：
  名称：

  Asymmetric Synthesis of Polyhydroxylated Pyrrolizidines via Transannular Iodoamination with Concomitant N-Debenzylation

  摘要：

  The doubly diastereoselective "matched" conjugate addition of lithium (R)-N-but-3-enyl-N-(alpha-methyl-p-methoxybenzyl)amide to tert-butyl (4S,5R,E)-4,5-O-isopropylidene-2,7-dienoate (derived from D-ribose in 3 steps) and in situ enolate oxidation with (-)-camphorsulfonyloxaziridine was followed by ring-closing metathesis with Grubbs 1 to give a hexahydroazocine scaffold. Subsequent treatment with I-2 resulted in transannular Iodoamination accompanied by loss of the alpha-methyl-p-methoxybenzyl group to give the corresponding pyrrolizidine scaffold as a single diastereoisomer upon direct crystallization from the crude reaction mixture. Further functional group manipulations enabled the preparation of (-)-7a-epi-hyacinthacine A1.

  DOI：

  10.1021/ol103090z

文献信息

• Asymmetric Synthesis of Polyhydroxylated Pyrrolizidines via Transannular Iodoamination with Concomitant <i>N</i>-Debenzylation
  作者：E. Anne Brock、Stephen G. Davies、James A. Lee、Paul M. Roberts、James E. Thomson

  DOI：10.1021/ol103090z

  日期：2011.4.1

  The doubly diastereoselective "matched" conjugate addition of lithium (R)-N-but-3-enyl-N-(alpha-methyl-p-methoxybenzyl)amide to tert-butyl (4S,5R,E)-4,5-O-isopropylidene-2,7-dienoate (derived from D-ribose in 3 steps) and in situ enolate oxidation with (-)-camphorsulfonyloxaziridine was followed by ring-closing metathesis with Grubbs 1 to give a hexahydroazocine scaffold. Subsequent treatment with I-2 resulted in transannular Iodoamination accompanied by loss of the alpha-methyl-p-methoxybenzyl group to give the corresponding pyrrolizidine scaffold as a single diastereoisomer upon direct crystallization from the crude reaction mixture. Further functional group manipulations enabled the preparation of (-)-7a-epi-hyacinthacine A1.