(4S,5R)-1,3-dibenzyl-5-(benzyloxycarbonyl)-2-oxo-imidazolidine-4-carboxylic acid | 104487-17-4

• 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: (4S,5R)-1,3-dibenzyl-5-(benzyloxycarbonyl)-2-oxo-imidazolidine-4-carboxylic acid
• 英文别名: (4S,5R)-1,3-dibenzyl-2-oxo-5-phenylmethoxycarbonylimidazolidine-4-carboxylic acid
• CAS: 104487-17-4
• 化学式: C₂₆H₂₄N₂O₅
• 分子量: 444.487
• InChiKey: JRCPQQJIEJDSSN-XZOQPEGZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  33
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  87.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  (4S,5R)-1,3-dibenzyl-1H-furo[3,4-d]imidazole-2,4,6-trione 、 苯甲醇 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-dibenzyl-5-(benzyloxycarbonyl)-2-oxo-imidazolidine-4-carboxylic acid 、 (4S,5R)-1,3-dibenzyl-5-(benzyloxycarbonyl)-2-oxo-imidazolidine-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

• Verfahren zur Herstellung von (3a5,6aR)-und/oder(3aR,6a5)-1,3-Dibenzyl-hexahydro-1H-furo(3,4-d)imidazol-2,4-dion
  申请人：MERCK PATENT GmbH

  公开号：EP0173185A1

  公开（公告）日：1986-03-05

  Racemische Halbester der Formel Ia/b worin R Alkyl mit 1 bis 6 C-Atomen, Alkoxyalkyl mit 2-8 C-Atomen, Cycloalkyl mit 3 bis 5 C-Atomen, Alkenyl mit 2 bis 6 C-Atomen, Benzyl oder 1- oder 2-Phenylethyl, BZL Benzyl bedeutet, lassen sich durch Salzbildung mit (+)-Dehydroabietyiamin und Kristallisation der Diastereomerensalzpaare trennen. Optisch aktive cis-1,3-Dibenzyl-5-alkoxycarbonyl-2-oxo- imidazolidin-4-carbonsäuren dienen als Zwischenprodukte zur Herstellung von D-(+)-Biotin. Diastereomere Salze aus einem optisch aktiven Amin und einer optisch aktiven 1,3-Dibenzyl-5-alkoxycarbonyl-2-oxo- imidazolidin-4-carbonsäure können zu optisch aktiven 1,3-Di- benzyl-hexahydro-1H-furo[3,4-d]imidazol-2,4-dionen reduziert werden, weiche als Zwischenprodukte zur Herstellung von D-(+)-Biotin dienen.

  式 Ia/b 的外消旋半酯 其中 R 表示 1 至 6 个 C 原子的烷基、2-8 个 C 原子的烷氧基烷基、3 至 5 个 C 原子的环烷基、2 至 6 个 C 原子的烯基、苄基或 1 或 2-苯基乙基，BZL 为苄基。 光学活性顺式-1,3-二苄基-5-烷氧羰基-2-氧代咪唑烷-4-羧酸是生产 D-(+)-生物素的中间体。 具有光学活性的胺和具有光学活性的 1,3-二苄基-5-烷氧羰基-2-氧代咪唑烷-4-羧酸的非对映异构盐可还原成具有光学活性的 1,3-二苄基六氢-1H-呋喃并[3,4-d]咪唑-2,4-二酮，作为制备 D-(+)-生物素的中间体。
• Verfahren zur Herstellung von Enantiomeren
  申请人：MERCK PATENT GmbH

  公开号：EP0226043A1

  公开（公告）日：1987-06-24

  Enantiomere optisch aktiver Dicarbonsäuremonoester lassen sich durch deren intramolekulare Umlagerung unter Drehsinnumkehr erhalten.

  光学活性二羧酸单酯的对映体可通过分子内旋转方向相反的重排获得。
• Total synthesis of (+)-biotin via a quinine-mediated asymmetric alcoholysis of meso-cyclic anhydride strategy
  作者：Jian Huang、Fei Xiong、Fen-Er Chen

  DOI：10.1016/j.tetasy.2008.05.020

  日期：2008.6

  A concise asymmetric total synthesis of (+)-biotin 1 has been accomplished in which the absolute stereochemistry of C-3a, C-6a of 1 was established by utilizing an efficient and practical quinine-mediated asymmetric alcoholysis of meso-cyclic anhydride 2 in a single step, the C-4 stereochemistry was installed by a direct stereoselective ionic hydrogenation of the thiolactol 7. (C) 2008 Elsevier Ltd. All rights reserved.
• US4739071A
  申请人：——

  公开号：US4739071A

  公开（公告）日：1988-04-19
• 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.