(2S,3S)-3-hydroxy-4-oxo-N-(9'-phenylfluoren-9'-yl)pyrrolidine-2-carboxylic acid methyl ester | 160882-77-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: (2S,3S)-3-hydroxy-4-oxo-N-(9'-phenylfluoren-9'-yl)pyrrolidine-2-carboxylic acid methyl ester
• 英文别名: methyl (2S,3S)-3-hydroxy-4-oxo-1-(9-phenylfluoren-9-yl)pyrrolidine-2-carboxylate
• CAS: 160882-77-9
• 化学式: C₂₅H₂₁NO₄
• 分子量: 399.446
• InChiKey: OKUVFRLMXBASFP-XZOQPEGZSA-N

物化性质

• 沸点：
  555.1±50.0 °C(Predicted)
• 密度：
  1.351±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  30
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  66.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2S,3S)-3-hydroxy-4-oxo-N-(9'-phenylfluoren-9'-yl)pyrrolidine-2-carboxylic acid methyl ester 在 palladium on activated charcoal 盐酸 、 lithium hydroxide 、 氢气 、 双氧水 、 三乙基硼氢化锂 作用下， 以 甲醇 为溶剂， -78.0 ℃ 、358.53 kPa 条件下， 反应 14.0h， 生成 (2R,3S,4R)-3,4-二羟基-2-(羟甲基)吡咯烷盐酸盐
  参考文献：
  名称：

  从反式-4-羟基-L-脯氨酸对映体和立体选择性合成多羟基化吡咯烷和吲哚并立定。

  摘要：

  我们从4-羟基-L-脯氨酸开始开发了一种多羟基化的吡咯烷和吲哚并立苷糖苷酶抑制剂的简短，有效和立体选择性的合成方法。N-Pf-4-氧代脯氨酸烯醇的区域和立体选择性羟基化以及所得酮醇的立体选择性还原使我们能够引入目标化合物中存在的顺式二醇。通过还原取代的脯氨酸的酯基或通过有机锂或有机镁试剂与相同基团的反应，然后立体选择性地还原所得的酮，来引入完成目标化合物合成所需的不同侧链。如此获得的醇经氢解得到所需吡咯烷糖苷酶抑制剂的盐酸盐，分九步获得，总收率超过50％。也使用该方法制备了吲哚唑烷糖苷酶抑制剂8-表-swainsonine。

  DOI：

  10.1021/jo9604245
• 作为产物：
  描述：

  9-溴-9-苯基芴 在 三甲基氯硅烷 、 lead(II) nitrate 、 草酰氯 、 MoO5*pyridine*HMPA 、 sodium hexamethyldisilazane 、 二甲基亚砜 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 102.0h， 生成 (2S,3S)-3-hydroxy-4-oxo-N-(9'-phenylfluoren-9'-yl)pyrrolidine-2-carboxylic acid methyl ester
  参考文献：
  名称：

  从反式-4-羟基-L-脯氨酸对映体和立体选择性合成多羟基化吡咯烷和吲哚并立定。

  摘要：

  我们从4-羟基-L-脯氨酸开始开发了一种多羟基化的吡咯烷和吲哚并立苷糖苷酶抑制剂的简短，有效和立体选择性的合成方法。N-Pf-4-氧代脯氨酸烯醇的区域和立体选择性羟基化以及所得酮醇的立体选择性还原使我们能够引入目标化合物中存在的顺式二醇。通过还原取代的脯氨酸的酯基或通过有机锂或有机镁试剂与相同基团的反应，然后立体选择性地还原所得的酮，来引入完成目标化合物合成所需的不同侧链。如此获得的醇经氢解得到所需吡咯烷糖苷酶抑制剂的盐酸盐，分九步获得，总收率超过50％。也使用该方法制备了吲哚唑烷糖苷酶抑制剂8-表-swainsonine。

  DOI：

  10.1021/jo9604245

文献信息

• Asymmetric synthesis of 3S, 4R-dihydroxypyrrolidines by regio- and stereoselective hydroxylation of 4-oxoproline enolate
  作者：M.Jesús Blanco、F.Javier Sardina

  DOI：10.1016/s0040-4039(00)74441-8

  日期：1994.11

  enantiomerically pure (2R, 3S, 4R) 3,4-dihydroxy-2-hydroxymethylpyrrolidine, a galactosidase inhibitor, from 4-hydroxy-L-proline is presented. The key steps are the regio- and stereoselective hydroxylation of a 4-oxoproline enolate and the stereoselective reduction of the resulting ketoalcohol. An N-(9-phenylfluoren-9-yl) moiety is used not only as an N-protecting group but as a regio- and stereochemical control

  提出了从4-羟基-L-脯氨酸的对映体纯的（2 R，3 S，4 R）3,4-二羟基-2-羟甲基吡咯烷酮（一种半乳糖苷酶抑制剂）的短而有效的立体选择性合成。关键步骤是4-氧代脯氨酸烯醇的区域和立体选择性羟基化以及所得酮醇的立体选择性还原。一个ñ - （9-苯基芴-9-基）部分不仅用作一个ñ -保护基团，但作为一个区域选择性和立体化学控制元件为好。
• Total Synthesis of Depsilairdin
  作者：Dale E. Ward、Sandip G. Pardeshi

  DOI：10.1021/jo1009239

  日期：2010.8.6

  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.
• C-3- and C-4-Alkylated Polyhydroxypyrrolidines:  Enantiospecific Syntheses and Glycosidase Inhibitory Activity
  作者：María-Jesús Blanco、F. Javier Sardina

  DOI：10.1021/jo980078m

  日期：1998.5.1

  Short, efficient, and stereoselective syntheses of enantiomerically pure C-3- and C-4-alkylated analogues of (2R,3S,4R)-3,4-dihydroxy-2-(hydroxymethyl) a potent alpha-galactosidase inhibitor, from 4-hydroxy-L-proline are presented. Grignard addition or enolate alkylation of a N-(9-phenylfluoren-9-yl)-4-oxo-3-[(methoxymethyl)oxy]proline and epoxidation or hydroboration of a 4-methylene-3-[(methoxymethyl)oxy]proline proceeded with complete stereoselection and in excellent yields. The inhibitory activities of the synthesized pyrrolidines were measured and showed that the fit of A. niger alpha-galactosidase and the jack bean alpha-mannosidase around C-3 of the pyrrolidine ring (alpha face) must be very tight, while the fit around C-4 (alpha face) is much looser. Positioning a methylene group between the hydroxyl at C-4 and the pyrrolidine ring completely abolishes the inhibitory activity (see analogue 5).
• Enantiospecific and Stereoselective Synthesis of Polyhydroxylated Pyrrolidines and Indolizidines from <i>trans</i>-4-Hydroxy-<scp>l</scp>-proline
  作者：María-Jesús Blanco、F. Javier Sardina

  DOI：10.1021/jo9604245

  日期：1996.1.1

  We have developed a short, efficient, and stereoselective synthesis of polyhydroxylated pyrrolidine and indolizidine glycosidase inhibitors starting from 4-hydroxy-L-proline. The regio- and stereoselective hydroxylation of an N-Pf-4-oxoproline enolate and the stereoselective reduction of the resulting keto alcohol allowed us to introduce the cis diol present in the target compounds. The different side

  我们从4-羟基-L-脯氨酸开始开发了一种多羟基化的吡咯烷和吲哚并立苷糖苷酶抑制剂的简短，有效和立体选择性的合成方法。N-Pf-4-氧代脯氨酸烯醇的区域和立体选择性羟基化以及所得酮醇的立体选择性还原使我们能够引入目标化合物中存在的顺式二醇。通过还原取代的脯氨酸的酯基或通过有机锂或有机镁试剂与相同基团的反应，然后立体选择性地还原所得的酮，来引入完成目标化合物合成所需的不同侧链。如此获得的醇经氢解得到所需吡咯烷糖苷酶抑制剂的盐酸盐，分九步获得，总收率超过50％。也使用该方法制备了吲哚唑烷糖苷酶抑制剂8-表-swainsonine。