benzyl N-[[4-(trifluoromethyl)phenyl]methylidene]carbamate | 1355742-48-1

• 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: benzyl N-[[4-(trifluoromethyl)phenyl]methylidene]carbamate
• CAS: 1355742-48-1
• 化学式: C₁₆H₁₂F₃NO₂
• 分子量: 307.272
• InChiKey: XMKMEVFGCQAZHB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  三甲基氰硅烷 、 benzyl N-[[4-(trifluoromethyl)phenyl]methylidene]carbamate 在 甲醇 、 [Li{Ru[(S)-phgly]2[(S)-binap]}]Cl 作用下， 以 甲基叔丁基醚 为溶剂， 反应 20.25h， 以93%的产率得到(+)-2-benzyloxycarbonylamino-2-(4-trifluoromethylphenyl)acetonitrile
  参考文献：
  名称：

  Enantioselective Hydrocyanation of N-Protected Aldimines

  摘要：

  Enantioselective hydrocyanation of N-benzyloxycarbonyl aldimines catalyzed by a Ru[(S)-phgly](2)[(S)-binap]/C6H5OLi system or a bimetallic complex [Li{Ru[(S)-phgly](2)[(S)-binap]}]Cl affords the amino nitriles in 92-99% ee. The reaction is carried out in tert-C4H9OCH3 with a substrate-to-catalyst molar ratio in the range of 500-5000 at -20 to 0 degrees C. Primary, secondary, and tertiary alkyl imines as well as the aryl and heteroaryl substrates are smoothly cyanated to produce the desired products in high yield.

  DOI：

  10.1021/ol203408w
• 作为产物：
  描述：

  benzyl {(phenylsulfonyl)[4-(trifluoromethyl)phenyl]methyl}carbamate 在 potassium carbonate 作用下， 以 二氯甲烷 为溶剂， 以91%的产率得到benzyl N-[[4-(trifluoromethyl)phenyl]methylidene]carbamate
  参考文献：
  名称：

  Diastereo- and Enantioselective Addition of Anilide-Functionalized Allenoates to N-Acylimines Catalyzed by a Pyridylalanine-Based Peptide

  摘要：

  A selective peptide-catalyzed addition of allenic esters to N-acylimines is reported. Tetrasubstituted allenes were achieved with up to 42:1 diastereomeric ratio and 94:6 enantiomeric ratio (up to 99:1 er after recrystallization of the major diastereomer). An exploration of the role of individual amino acids within the peptide was undertaken. The scope of the reaction was explored and revealed heightened reactivity with thioester-containing allenes. A mechanistic framework that may account for the observed reactivity is also described.

  DOI：

  10.1021/ja412996f

文献信息

• Direct asymmetric Mannich reaction of phthalides: facile access to chiral substituted isoquinolines and isoquinolinones
  作者：Jie Luo、Haifei Wang、Fangrui Zhong、Jacek Kwiatkowski、Li-Wen Xu、Yixin Lu

  DOI：10.1039/c2cc31439h

  日期：——

  The first Mannich reaction employing phthalides using a quinidine-based multifunctional catalyst has been developed. The reported method led to the synthesis of 3,3-disubstituted phthalide derivatives in excellent yields, with good diastereo- and enantioselectivities. Convenient synthesis of chiral isoquinolinones and isoquinolines has also been demonstrated.

  首次利用基于奎尼丁的多功能催化剂进行邻苯二甲酸内酯的Mannich反应已被开发。所报道的方法合成了3,3-二取代的邻苯二甲酸内酯衍生物，产率极高，且具有良好的非对映选择性和对映选择性。此外，便捷合成手性异喹啉酮和异喹啉的示例也已得到证明。
• Enantio- and Diastereoselective Mannich Reactions of ß-Dicarbonyls by Second Stage Diastereoconvergent Crystallization
  作者：William R. Cassels、Evan T. Crawford、Jeffrey S. Johnson

  DOI：10.1021/acscatal.3c01515

  日期：2023.5.19

  The synthesis of chiral α-monosubstituted-ß-dicarbonyls is a challenging task in asymmetric catalysis due to the rapid, typically uncontrolled, product racemization or epimerization under most reaction conditions. For this reason, diastereoselective additions of unsubstituted ß-dicarbonyls to π-electrophiles are unusual. Herein, we disclose a simple catalytic crystallization-driven enantio- and diastereoselective

  手性 α-单取代-β-二羰基的合成在不对称催化中是一项具有挑战性的任务，因为在大多数反应条件下，产物会发生快速且通常不受控制的外消旋或差向异构化。因此，未取代的 β-二羰基与 π-亲电子试剂的非对映选择性加成是不常见的。在此，我们公开了一种简单的催化结晶驱动的对映和非对映选择性曼尼希反应，用于合成立体定义的α-单取代-β-酮酯、不对称β-二酯、不对称β-二酮和β-酮​​酰胺，该反应有效地利用产物差向异构化在溶液中。机理研究表明，最初的对映选择性、非对映发散骨架组装是由手性叔胺有机催化剂催化的，然后促进第二阶段结晶诱导的非对映会聚，以提供具有优异立体选择性的具有挑战性的α-立构中心。