methyl (2S,3S,4R)-4-(tert-butyldimethylsilyloxy)-3-(methoxymethoxy)-3-methyl-pyrrolidine-2-carboxylate | 1236783-65-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: methyl (2S,3S,4R)-4-(tert-butyldimethylsilyloxy)-3-(methoxymethoxy)-3-methyl-pyrrolidine-2-carboxylate
• 英文别名: [(4-O-TBS)(3-O-MOM)Dhmp-OMe]；methyl (2S,3S,4R)-4-[tert-butyl(dimethyl)silyl]oxy-3-(methoxymethoxy)-3-methylpyrrolidine-2-carboxylate
• CAS: 1236783-65-5
• 化学式: C₁₅H₃₁NO₅Si
• 分子量: 333.5
• InChiKey: CPUWYFOIJDRWEN-LALPHHSUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  66
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  N-苄氧羰基-N-甲基-L-缬氨酸 、 methyl (2S,3S,4R)-4-(tert-butyldimethylsilyloxy)-3-(methoxymethoxy)-3-methyl-pyrrolidine-2-carboxylate 在 N,N-二异丙基乙胺 、 bromo-tris(1-pyrrolidinyl)phosphonium hexafluorophosphate 作用下， 以 二氯甲烷 为溶剂， 反应 18.17h， 以0.27 g的产率得到Cbz-MeVal-(4-O-TBS)(3-O-MOM)Dhmp-OMe
  参考文献：
  名称：

  Total Synthesis of Depsilairdin

  摘要：

  The total synthesis of depsilairdin, a host-selective phytotoxin isolated from Leptosphaeria maculans (the causal agent of blackleg disease of oilseed Brassicas), has been achieved by N-terminal extension of a suitably protected derivative of the hitherto unknown amino acid (2S,3S,4R)-3,4-dihydroxy-3-methyl-proline (Dhmp) followed by esterification with lairdinol A. The latter esterification, complicated by the sterically hindered nature of the carboxyl group, was accomplished by a novel method involving reaction of the 1-hydroxybenzotriazole (HOBt) derived active ester with the bromomagnesium alkoxide of lairdinol A. Three depsilairdin analogues were also prepared by replacing the Dhmp residue with L-proline and cis- and trans-4-hydroxy-L-proline. Phytotoxicity assays showed that the analogues were nontoxic to both blackleg-susceptible (brown mustard) and -resistant (canola) plants, suggesting that the presence of the Dhmp residue in depsilairdin is important for its host-selective toxicity toward brown mustard.

  DOI：

  10.1021/jo1009239
• 作为产物：
  描述：

  methyl (2S,3S,4R)-4-(tert-butyldimethylsilyloxy)-3-(methoxymethoxy)-3-methyl-1-(9-phenyl-9H-fluoren-9-yl)pyrrolidine-2-carboxylate 在 palladium 10% on activated carbon 、 氢气 作用下， 以 异丙醇 为溶剂， 反应 6.0h， 生成 methyl (2S,3S,4R)-4-(tert-butyldimethylsilyloxy)-3-(methoxymethoxy)-3-methyl-pyrrolidine-2-carboxylate
  参考文献：
  名称：

  Total Synthesis of Depsilairdin

  摘要：

  The total synthesis of depsilairdin, a host-selective phytotoxin isolated from Leptosphaeria maculans (the causal agent of blackleg disease of oilseed Brassicas), has been achieved by N-terminal extension of a suitably protected derivative of the hitherto unknown amino acid (2S,3S,4R)-3,4-dihydroxy-3-methyl-proline (Dhmp) followed by esterification with lairdinol A. The latter esterification, complicated by the sterically hindered nature of the carboxyl group, was accomplished by a novel method involving reaction of the 1-hydroxybenzotriazole (HOBt) derived active ester with the bromomagnesium alkoxide of lairdinol A. Three depsilairdin analogues were also prepared by replacing the Dhmp residue with L-proline and cis- and trans-4-hydroxy-L-proline. Phytotoxicity assays showed that the analogues were nontoxic to both blackleg-susceptible (brown mustard) and -resistant (canola) plants, suggesting that the presence of the Dhmp residue in depsilairdin is important for its host-selective toxicity toward brown mustard.

  DOI：

  10.1021/jo1009239