O-(2-methacryloyloxyethylsuccinoyl)-trans-4-hydroxy-α,α-di-phenyl-L-prolinol | 1173148-10-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: O-(2-methacryloyloxyethylsuccinoyl)-trans-4-hydroxy-α,α-di-phenyl-L-prolinol
• 英文别名: 4-O-[(3R,5S)-5-[hydroxy(diphenyl)methyl]pyrrolidin-3-yl] 1-O-[2-(2-methylprop-2-enoyloxy)ethyl] butanedioate
• CAS: 1173148-10-1
• 化学式: C₂₇H₃₁NO₇
• 分子量: 481.546
• InChiKey: MSEXZJWBNJEGGX-PKTZIBPZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  35
• 可旋转键数：
  14
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  111
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  O-(2-methacryloyloxyethylsuccinoyl)-trans-4-hydroxy-α,α-di-phenyl-L-prolinol hydrochloride 在 potassium carbonate 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 0.08h， 以100%的产率得到O-(2-methacryloyloxyethylsuccinoyl)-trans-4-hydroxy-α,α-di-phenyl-L-prolinol
  参考文献：
  名称：

  Enantioselectivity, swelling and stability of 4-hydroxyprolinol containing acrylic polymer beads in the asymmetric reduction of ketones

  摘要：

  A new 4-hydroxy-alpha,alpha-diphenyl-L-prolinol containing polymethacrylate, prepared without chromatography by a large scale adaptable synthesis, has been evaluated as a catalyst in the asymmetric reduction of 1-arylethanones. Using 1-(4-bromophenyl)ethanone as the model substance, the reduction was tested with various borane sources and solvents. The best swellings of the polymer and reactivity were observed in THF using N,N-diethylaniline borane complex as the hydride source. The selectivity in the reduction of 1-(4-bromophenyl)ethanone was found to depend on the substrate concentration and catalyst loading. Using the best conditions identified, a series of 1-arylethanones was reduced to their corresponding enantioenriched secondary alcohols. High rates and ee-values were obtained in the reduction of acetophenones containing electron withdrawing groups in the aromatic ring, whereas a moderate selectivity was the result for products containing electron donating aromatic substituents. Upon recovery of the polymer beads, it was found that vacuum drying led to extensive rupturing, while the bead structure was intact if washed with methanol and air dried at atmospheric pressure. Repeated use of the polymer catalyst gave the product alcohol with a lower 90% ee. Elemental analysis showed this to be due to the loss of the chiral prolinol unit. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2011.12.001

文献信息

• POLYMER ORGANOCATALYST AND PREPARATION PROCESS
  申请人：Hansen Tore

  公开号：US20110034654A1

  公开（公告）日：2011-02-10

  A chiral polymer organocatalyst comprising a main chain and side chain organocatalytic groups covalently attached to the main chain, which organocatalytic groups comprise an amino acid or amino acid derivative of the following general formula (I), in which one stereoisomeric form predominates: formula (I) wherein the catalyst is bound to the polymer main chain via R 1 , R 2 , R 4 , R 5 or R 6 through a linker (L) or direct bond, and wherein R 1 -R 6 and Z are defined as follows: R 1 is H, a naturally occurring alpha-amino acid side chain or a non-natural commercially available alpha-amino acid side chain that may contain L; R 2 is H, O (doubly bonded to give a carbonyl), O-L (where L is a linker), NH-L or L; R 3 is H or doubly bonded to give a carbonyl with R 2 when R 2 is O; R 4 is H, C 1 -C 6 alkyl or L R 5 is H, CO 2 H, C 1 -C 6 alkyl, benzyl, L, CONHR (in which R is alkyl, aryl, heteroaryl, arylalkyl or, heteroarylalkyl), tetrazolyl, CH2 coupled to a triazole moiety, an esterified CH 2 OH or CO 2 R (in which R is alkyl, aryl, heteroaryl, arylalkyl N or heteroarylalkyl), formula (II) or formula (III) wherein z is formula (IV) or a directed bond, X 4 is H, Me 3 Si or Et 3 Si, X 3 comprises a naturally-occurring alpha-amino acid side chain, H, C 1 -C 6 alkyl or phenyl, Ar 1 and Ar 2 are each independently aryl or heteroaryl, and Y denotes the position of attachment to the main chain or linker; and R 6 is H, CO 2 H3 C 1 -C 6 alkyl, benzyl or L; and wherein the polymer organocatalyst comprises a cross-linked polymer.

  手性聚合物有机催化剂，包括主链和侧链有机催化基团，这些有机催化基团通过共价键连接到主链上，其中所述有机催化基团包括以下通式（I）的氨基酸或氨基酸衍生物，其中一种立体异构体占优势：通式（I），其中催化剂通过连接物（L）或直接键与聚合物主链通过R1、R2、R4、R5或R6结合，其中R1-R6和Z的定义如下：R1为H，天然存在的α-氨基酸侧链或非天然商业可得的α-氨基酸侧链，可能包含L；R2为H，O（双键形成羰基），O-L（其中L为连接物），NH-L或L；当R2为O时，R3为H或与R2形成双键形成羰基；R4为H，C1-C6烷基或L；R5为H，CO2H，C1-C6烷基，苄基，L，CONHR（其中R为烷基、芳基、杂芳基、芳基烷基或杂芳基烷基），四唑基，与三唑基结合的CH2，酯化的 OH或CO2R（其中R为烷基、芳基、杂芳基、芳基烷基、N或杂芳基烷基），通式（II）或通式（III），其中z为通式（IV）或直接键，X4为H、Me3Si或Et3Si，X3包括天然存在的α-氨基酸侧链、H、C1-C6烷基或苯基，Ar1和Ar2各自独立地为芳基或杂芳基，Y表示与主链或连接物的连接位置；R6为H、CO2H、C1-C6烷基、苄基或L；聚合物有机催化剂包括交联聚合物。