(4R,5S)-1,3-dibenzylimidazolidin-2-one-4,5-dicarboxylic acid monocyclohexyl ester

• 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: (4R,5S)-1,3-dibenzylimidazolidin-2-one-4,5-dicarboxylic acid monocyclohexyl ester
• 英文别名: (4S,5R)-1,3-dibenzyl-5-(cyclohexyloxycarbonyl)-2-oxoimidazolidine-4-carboxylic acid；(4S,5R)-1,3-dibenzyl-5-cyclohexyloxycarbonyl-2-oxoimidazolidine-4-carboxylic acid
• 化学式: C₂₅H₂₈N₂O₅
• 分子量: 436.508
• InChiKey: CBZIUCQMNDNHRQ-FCHUYYIVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  32
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  87.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (4R,5S)-1,3-dibenzylimidazolidin-2-one-4,5-dicarboxylic acid monocyclohexyl ester 在 sodium hydroxide 、 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 5.0h， 生成 (4S,5S)-1,3-dibenzylimidazolidin-2-one-4,5-dicarboxylic acid
  参考文献：
  名称：

  含咪唑烷基-2-酮骨架的非对映异构体1,4-二膦配体的合成及其在Rh（I）催化的功能化烯烃不对称加氢中的应用

  摘要：

  非对映体1,4-二膦配体（S，S，S，S）-1a，（R，S，S，R）-1b和（R，S，S，S）-1c，含咪唑啉二-2合成一个骨架，并将其用于研究骨架手性对Rh（I）催化的各种官能化烯烃底物加氢中对映选择性的影响。已经发现，催化效率在很大程度上取决于α-碳到膦的构型。因此，伪c ^ 2 -symmetrical二膦，（- [R ，小号，小号，小号） - 1C，表明在基片，特别是在甲基α-的氢化的广谱的氢化优异的对映选择性（93.0-98.6％EES）（ñ -乙酰胺基）-β-芳基丙烯酸酯（95.3–97.0％ee）。但是，通过C 2对称的（R，S，S，R）-1b获得的对映选择性很大程度上取决于底物（19.8–97.3％ee）。配位体的铑配合物1a中具有（小号，小号，S，S）-构型显示了所有被检测底物的最低催化效率（0-84.8％ee）。

  DOI：

  10.1002/adsc.200404286
• 作为产物：
  描述：

  (4S,5R)-1,3-dibenzyl-1H-furo[3,4-d]imidazole-2,4,6-trione 、 环己醇 在 N-[(8Α,9S)-6'-甲氧基奎宁-9-基]-3,5-双(三氟甲基)苯亚磺酰胺 作用下， 以 甲基叔丁基醚 为溶剂， 生成 (4R,5S)-1,3-dibenzylimidazolidin-2-one-4,5-dicarboxylic acid monocyclohexyl ester 、 1,3-dibenzyl-5-(cyclohexyloxycarbonyl)-2-oxoimidazolidine-4-carboxylic acid
  参考文献：
  名称：

  An improved asymmetric total synthesis of (+)-biotin via the enantioselective desymmetrization of a meso-cyclic anhydride mediated by cinchona alkaloid-based sulfonamide

  摘要：

  The highly enantioselective total synthesis of (+)-biotin 1 via the Hoffmann-Roche lactone-thiolactone strategy has been achieved starting from cis-1,3-dibenzyl-2-imidazolidone-4,5-dicarboxylic acid 2 with an overall yield of 35%. Two contiguous stereogenic centers at C-3a and C-6a were established through a rapid cinchona alkaloid-based sulfonamide-mediated enantioselective alcoholysis of meso-cyclic anhydride 3 to afford (4S,5R)-cinnamyl hemiester 4h, the direct precursor to (3aS,6aR)-lactone 5 with high enantioselectivity. A one-pot installation of the 4-carboxybutyl side chain was accomplished by a Fukuyama coupling reaction of (3aS,6aR)-thiolactone 6 with the organozinc reagent prepared from ethyl 5-bromopentanoate. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2010.03.041

文献信息

• Preparation of optically active cis-1,3-dibenzyl-hexahydro-1H-furo(3,4-d)imidazole-2,4-dione and its intermediates
  申请人：SUMITOMO CHEMICAL COMPANY, LIMITED

  公开号：EP0084892B1

  公开（公告）日：1987-12-23
• US4496739A
  申请人：——

  公开号：US4496739A

  公开（公告）日：1985-01-29
• US4544635A
  申请人：——

  公开号：US4544635A

  公开（公告）日：1985-10-01
• Synthesis of Diastereomeric 1,4-Diphosphine Ligands Bearing Imidazolidin-2-one Backbone and Their Application in Rh(I)-Catalyzed Asymmetric Hydrogenation of Functionalized Olefins
  作者：Yong?Jian Zhang、Kee?Yong Kim、Jung?Hwan Park、Choong?Eui Song、Kyungae Lee、Myoung?Soo Lah、Sang-gi Lee

  DOI：10.1002/adsc.200404286

  日期：2005.3

  The diastereomeric 1,4-diphosphine ligands, (S,S,S,S)-1a, (R,S,S,R)-1b and (R,S,S,S)-1c, with the imidazolidin-2-one backbone were synthesized, and utilized for an investigation of the effects of backbone chirality on the enantioselectivity in the Rh(I)-catalyzed hydrogenation of various functionalized olefinic substrates. It was found that the catalytic efficiencies are largely dependent on the configurations

  非对映体1,4-二膦配体（S，S，S，S）-1a，（R，S，S，R）-1b和（R，S，S，S）-1c，含咪唑啉二-2合成一个骨架，并将其用于研究骨架手性对Rh（I）催化的各种官能化烯烃底物加氢中对映选择性的影响。已经发现，催化效率在很大程度上取决于α-碳到膦的构型。因此，伪c ^ 2 -symmetrical二膦，（- [R ，小号，小号，小号） - 1C，表明在基片，特别是在甲基α-的氢化的广谱的氢化优异的对映选择性（93.0-98.6％EES）（ñ -乙酰胺基）-β-芳基丙烯酸酯（95.3–97.0％ee）。但是，通过C 2对称的（R，S，S，R）-1b获得的对映选择性很大程度上取决于底物（19.8–97.3％ee）。配位体的铑配合物1a中具有（小号，小号，S，S）-构型显示了所有被检测底物的最低催化效率（0-84.8％ee）。
• An improved asymmetric total synthesis of (+)-biotin via the enantioselective desymmetrization of a meso-cyclic anhydride mediated by cinchona alkaloid-based sulfonamide
  作者：Fei Xiong、Xu-Xiang Chen、Fen-Er Chen

  DOI：10.1016/j.tetasy.2010.03.041

  日期：2010.4

  The highly enantioselective total synthesis of (+)-biotin 1 via the Hoffmann-Roche lactone-thiolactone strategy has been achieved starting from cis-1,3-dibenzyl-2-imidazolidone-4,5-dicarboxylic acid 2 with an overall yield of 35%. Two contiguous stereogenic centers at C-3a and C-6a were established through a rapid cinchona alkaloid-based sulfonamide-mediated enantioselective alcoholysis of meso-cyclic anhydride 3 to afford (4S,5R)-cinnamyl hemiester 4h, the direct precursor to (3aS,6aR)-lactone 5 with high enantioselectivity. A one-pot installation of the 4-carboxybutyl side chain was accomplished by a Fukuyama coupling reaction of (3aS,6aR)-thiolactone 6 with the organozinc reagent prepared from ethyl 5-bromopentanoate. (C) 2010 Elsevier Ltd. All rights reserved.