(R)-dibenzyl 1-(1-hydroxybutan-2-yl)hydrazine-1,2-dicarboxylate | 1215035-93-0

• 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: (R)-dibenzyl 1-(1-hydroxybutan-2-yl)hydrazine-1,2-dicarboxylate
• 英文别名: dibenzyl 1-(1-hydroxybutan-2-yl)hydrazine-1,2-dicarboxylate；benzyl N-[(2R)-1-hydroxybutan-2-yl]-N-(phenylmethoxycarbonylamino)carbamate
• CAS: 1215035-93-0
• 化学式: C₂₀H₂₄N₂O₅
• 分子量: 372.421
• InChiKey: GBKXZNFFILMGED-GOSISDBHSA-N

物化性质

• 密度：
  1.229±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  27
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  88.1
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  偶氮二甲酸二苄酯 在 sodium tetrahydroborate 作用下， 以 乙醇 、 氯仿 为溶剂， 20.0 ℃ 、6.0 MPa 条件下， 反应 0.25h， 生成 (R)-dibenzyl 1-(1-hydroxybutan-2-yl)hydrazine-1,2-dicarboxylate
  参考文献：
  名称：

  连续流反应器中异相二肽催化醛的α-胺化：停留时间对对映选择性的影响

  摘要：

  开发了固相支持的二肽催化连续流工艺，用于以偶氮二羧酸二苄酯为亲电氮源直接对醛进行对映选择性α-胺化反应。利用停留时间控制作为微调对映选择性的有效工具，可以以优异的ee值获得合成有用的α-肼基醇。填充床系统被证明是高度耐用的：在整个连续流操作20小时内，未发现催化剂活性或选择性下降。

  DOI：

  10.1002/adsc.201500375

文献信息

• ORGANOCATALYST
  申请人：Chen Kwunmin

  公开号：US20110040104A1

  公开（公告）日：2011-02-17

  The present invention provides an organocatalyst of formula (I), wherein R 1 is —H, —OH, —O—Si(R 4 )(R 5 )(R 6 ) or C 1-6 alkoxy, in which R 4 , R 5 and R 6 are identical or different and independently selected from the group consisting of C 1-6 alkyl, phenyl and phenyl substituted with C 1-6 alkyl; R 2 is —OH or ═O; X 1 is one selected from the group consisting of —NH—, —S— and X 2 is one selected from the group consisting of —C(═O)—, —CH 2 — and and X 1 is different from X 2 . The high yield and enantioselectivity of an addition reaction are obtained by using the organocatalyst of the present invention.

  本发明提供了一种式(I)的有机催化剂，其中R1为—H，—OH，—O—Si(R4)(R5)(R6)或C1-6烷氧基，其中R4、R5和R6相同或不同，并且独立地选自由C1-6烷基、苯基和苯基上取代的C1-6烷基的群；R2为—OH或═O；X1为从—NH—、—S—中选择的一种；X2为从—C(═O)—、—CH2—中选择的一种；X1与X2不同。通过使用本发明的有机催化剂，可以获得加成反应的高产率和对映选择性。
• Asymmetric Catalysis with a Mechanically Point-Chiral Rotaxane
  作者：Yusuf Cakmak、Sundus Erbas-Cakmak、David A. Leigh

  DOI：10.1021/jacs.6b00303

  日期：2016.2.17

  Mechanical point-chirality in a [2]rotaxane is utilized for asymmetric catalysis. Stable enantiomers of the rotaxane result from a bulky group in the middle of the thread preventing a benzylic amide macrocycle shuttling between different sides of a prochiral center, creating point chirality in the vicinity of a secondary amine group. The resulting mechanochirogenesis delivers enantioselective organocatalysis

  [2] 轮烷中的机械点手性用于不对称催化。轮烷的稳定对映异构体源于线中间的庞大基团，防止苄基酰胺大环在前手性中心的不同侧之间穿梭，在仲胺基团附近产生点手性。由此产生的机械手化通过烯胺（高达 71:29 er）和亚胺（高达 68:32 er）激活模式提供对映选择性有机催化。
• Remarkable Reaction Rate and Excellent Enantioselective Direct α-Amination of Aldehydes with Azodicarboxylates Catalyzed by Pyrrolidinylcamphor-Derived Organocatalysts
  作者：Pang-Min Liu、Chihliang Chang、Raju Jannapu Reddy、Ying-Fang Ting、Hsuan-Hao Kuan、Kwunmin Chen

  DOI：10.1002/ejoc.200901151

  日期：2010.1

  Remarkable reaction rate and excellent enantioselective direct α-amination of unmodified aldehydes with various azodicarboxylates was catalyzed by pyrrolidinylcamphor organo-catalyst 2a (5 mol-%) to provide the desired aminated products with excellent chemical yields and high to excellent levels of enantioselectivity (up to >99%ee) at 0 °C in CH 2 Cl 2 .

  由吡咯烷基樟脑有机催化剂 2a (5 mol-%) 催化未改性醛与各种偶氮二羧酸酯的显着反应速率和优异的对映选择性直接 α-胺化，以提供所需的胺化产物，具有优异的化学产率和高至优异的对映选择性水平（高达>99%ee) 在 0 °C 的 CH 2 Cl 2 中。
• Direct asymmetric α-amination of aldehydes with azodicarboxylates in ionic liquids catalyzed by imidazolium ion-tagged proline organocatalyst
  作者：Xiong Ding、Hong-Lai Jiang、Cheng-Jian Zhu、Yi-Xiang Cheng

  DOI：10.1016/j.tetlet.2010.09.036

  日期：2010.11

  Direct asymmetric α-amination of unmodified aldehydes with azodicarboxylates in ionic liquids in the presence of imidazolium ion-tagged l-proline organocatalyst 1 gives excellent enantioselectivities (up to 98% ee) and high chemical yields. The system can be easily recycled and reused for at least four times without significant loss of yields and enantioselectivity.

  在咪唑鎓离子标记的1-脯氨酸有机催化剂1存在下，离子液体中的未改性醛与偶氮二羧酸酯的直接不对称α胺化反应具有出色的对映选择性（高达98％ee）和高化学产率。该系统可以轻松地回收和再利用至少四次，而不会显着损失产率和对映选择性。
• Heterogeneous Dipeptide-Catalyzed α-Amination of Aldehydes in a Continuous-Flow Reactor: Effect of Residence Time on Enantioselectivity
  作者：Sándor B. Ötvös、Aliz Szloszár、István M. Mándity、Ferenc Fülöp

  DOI：10.1002/adsc.201500375

  日期：2015.11.16

  A solid-supported dipeptide-catalyzed continuous-flow process was developed for the direct enantioselective α-amination of aldehydes with dibenzyl azodicarboxylate as the electrophilic nitrogen source. With residence time control as an efficient tool for the fine-tuning of the enantioselectivity, synthetically useful α-hydrazino alcohols were achieved with excellent ees. The packed-bed system proved

  开发了固相支持的二肽催化连续流工艺，用于以偶氮二羧酸二苄酯为亲电氮源直接对醛进行对映选择性α-胺化反应。利用停留时间控制作为微调对映选择性的有效工具，可以以优异的ee值获得合成有用的α-肼基醇。填充床系统被证明是高度耐用的：在整个连续流操作20小时内，未发现催化剂活性或选择性下降。