dimethyl (2S,3S)-2-azido-3-(9-phenyl-9H-fluoren-9-ylamino)succinate | 159434-59-0

• 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: dimethyl (2S,3S)-2-azido-3-(9-phenyl-9H-fluoren-9-ylamino)succinate
• 英文别名: dimethyl (2S,3S)-2-azido-3-[(9-phenylfluoren-9-yl)amino]butanedioate
• CAS: 159434-59-0
• 化学式: C₂₅H₂₂N₄O₄
• 分子量: 442.474
• InChiKey: QYBNHSOVNSVJAU-VXKWHMMOSA-N

物化性质

• 熔点：
  150.5-151.5 °C(Solvent: Hexane; Ethyl acetate)

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  33
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  79
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  dimethyl (2S,3S)-2-azido-3-(9-phenyl-9H-fluoren-9-ylamino)succinate 在 palladium-barium carbonate 4-二甲氨基吡啶 、 氢气 、 sodium carbonate 作用下， 以 吡啶 、 甲醇 、 二氯甲烷 、 水 为溶剂， 70.0 ℃ 、101.33 kPa 条件下， 生成 (4S,5S)-1-benzyl-2-oxo-3-(9'-phenylfluoren-9'-yl)imidazolidine-4,5-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  对映体合成γ-酮-α，β-二氨基酸衍生物。链烷内酰胺前体的立体选择性合成

  摘要：

  二甲基（4S，5S）-1-苄基-2-氧代-3-（9″-苯基芴-9″-基）-咪唑烷-4,5-二羧酸酯（3）与几种有机锂试剂的反应得到相应的对映体纯的单酮（4a-e），收率好至极好。最终，将氯甲基酮4b转化为脲基酰胺8，它掺入了链霉菌素抗生素的一个组成部分链霉菌内酰胺（1）的双环核心。

  DOI：

  10.1016/s0040-4039(96)02389-1
• 作为产物：
  描述：

  dimethyl (S)-N-(9-phenyl-9H-fluoren-9-yl)aspartate 在 双(三甲基硅烷基)氨基钾 、 2,4,6-三异丙基苯磺酰叠氮化物 、 溶剂黄146 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 3.1h， 以40%的产率得到dimethyl (2S,3S)-2-azido-3-(9-phenyl-9H-fluoren-9-ylamino)succinate
  参考文献：
  名称：

  新型N-磺酰化（S，S）-2,3-二氨基琥珀酸酯型手性助剂的制备及其在腈类化合物与烯丙醇的不对称1,3-偶极环加成反应中的应用

  摘要：

  由L-天冬氨酸合成了新型的N-磺酰化（S，S）-2,3-二氨基琥珀酸酯型手性助剂，其具有酒石酸样骨架，并带有磺酰胺基而不是羟基。将合成的（S，S）-2,3-二氨基琥珀酸酯衍生物应用于腈类化合物与烯丙醇的不对称1,3-偶极环加成反应中，得到相应的旋光性2-异恶唑啉，对映选择性高达73％ ee。通过使用酒石酸二异丙酯作为手性助剂，对脸部的分化与之截然相反。

  DOI：

  10.1016/j.tetasy.2006.11.031

文献信息

• Enantiomerically Pure Highly Functionalized α-Amino Ketones from the Reaction of Chiral Cyclic <i>N</i>-(9-Phenylfluoren-9-yl) α-Amido Esters with Organolithium Reagents
  作者：Eduardo Fernández-Megía、José M. Iglesias-Pintos、F. Javier Sardina

  DOI：10.1021/jo970277q

  日期：1997.7.1

  The reaction of methyl N-(9-phenylfluoren-9-yl)pyroglutamate with several organolithium reagents afforded the corresponding ketones in excellent yields and with complete retention of enantiomeric purity. The success of this transformation is due to the unusual stability of the tetrahedral intermediates 5, which stems from two factors: the electron-withdrawing effect of the amide nitrogen and the Lithium complexing ability of the fluorenyl ring of the 9-phenylfluoren-9-yl group, This ester-to-ketone transformation was also successfully applied to oxazolidinone 9 and imidazolidinone 20 and provided a ketone (21b) that was ultimately transformed inter the urea-lactam 26 which incorporates the bicyclic core of streptolidine lactam, a component of the streptrothricin antibiotics.
• On the Stereoselectivity of the Reaction of N-(9-Phenylfluoren-9-yl)aspartate Enolates with Electrophiles. Synthesis of Enantiomerically Pure 3-Hydroxy-, 3-Amino-, and 3-Hydroxy-3-methylaspartates
  作者：Eduardo Fernandez-Megia、Manuel M. Paz、F. Javier Sardina

  DOI：10.1021/jo00104a019

  日期：1994.12

  We have developed efficient and stereoselective preparations of enantiomerically pure (3R)- and (3S)-N-Pf-3-hydroxy- and N-Pf-3-aminoaspartates by reaction of N-Pf-aspartate enolates with electrophilic hydroxylating or aminating reagents. The stereoselectivity of the hydroxylation and amination reactions was shown to be dependent on the structure of the enolate (which is strongly affected by the presence of strong metal complexing agents) and whether the electrophile is able to complex the enolate counterion in the transition state of the reaction. We have also developed a regioselective preparation of enantiomerically pure N-Pf-3-hydroxy-3-methylaspartates, albeit with only modest stereoselectivity.
• Enantiospecific synthesis of γ-keto-α,β-diamino acid derivatives. Stereoselective synthesis of a precursor of streptolidine lactam
  作者：Eduardo Fernández-Megía、F. Javier Sardina

  DOI：10.1016/s0040-4039(96)02389-1

  日期：1997.1

  The reaction of dimethyl (4S,5S)-1-benzyl-2-oxo-3-(9″-phenylfluoren-9″-yl)-imidazolidine-4,5-dicarboxylate (3) with several organolithium reagents afforded the corresponding enantiomerically pure monoketones (4a-e) in good to excellent yields. Chloromethyl-ketone 4b was ultimately transformed into ureido-amide 8 which incorporates the bicyclic core of streptolidine lactam (1), a component of the streptrothricin

  二甲基（4S，5S）-1-苄基-2-氧代-3-（9″-苯基芴-9″-基）-咪唑烷-4,5-二羧酸酯（3）与几种有机锂试剂的反应得到相应的对映体纯的单酮（4a-e），收率好至极好。最终，将氯甲基酮4b转化为脲基酰胺8，它掺入了链霉菌素抗生素的一个组成部分链霉菌内酰胺（1）的双环核心。
• Preparation of novel N-sulfonylated (S,S)-2,3-diaminosuccinate-type chiral auxiliaries and application to an asymmetric 1,3-dipolar cycloaddition reaction of nitrile oxides to allyl alcohol
  作者：Masakazu Serizawa、Yutaka Ukaji、Katsuhiko Inomata

  DOI：10.1016/j.tetasy.2006.11.031

  日期：2006.11

  Novel N-sulfonylated (S,S)-2,3-diaminosuccinate-type chiral auxiliaries, which have the tartaric acid-like framework with a sulfonamide group instead of a hydroxyl group, were synthesized from l-aspartic acid. The synthesized (S,S)-2,3-diaminosuccinate derivatives were applied to an asymmetric 1,3-dipolar cycloaddition reaction of nitrile oxides to allyl alcohol to afford the corresponding optically

  由L-天冬氨酸合成了新型的N-磺酰化（S，S）-2,3-二氨基琥珀酸酯型手性助剂，其具有酒石酸样骨架，并带有磺酰胺基而不是羟基。将合成的（S，S）-2,3-二氨基琥珀酸酯衍生物应用于腈类化合物与烯丙醇的不对称1,3-偶极环加成反应中，得到相应的旋光性2-异恶唑啉，对映选择性高达73％ ee。通过使用酒石酸二异丙酯作为手性助剂，对脸部的分化与之截然相反。