(S)-2-(4-tert-Butyl-phenyl)-propionaldehyde | 1793093-93-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (S)-2-(4-tert-Butyl-phenyl)-propionaldehyde
• 英文别名: (2S)-2-(4-tert-butylphenyl)propanal
• CAS: 1793093-93-2
• 化学式: C₁₃H₁₈O
• 分子量: 190.285
• InChiKey: SNOVXNPIRUDJNG-SNVBAGLBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  一氧化碳 、 4-叔丁基苯乙烯 在 (acetylacetonato)dicarbonylrhodium (l) 、 (2S)-8-[(2R,5R)-2,5-dimethylphospholan-1-yl]-1-{(11bR)-dinaphtho[2,1-d:1’,2’-f][1,3,2]dioxaphosphepin-4-yl}-2-(naphthalen-1-yl)-1,2-dihydroquinoline 、 氢气 作用下， 20.0 ℃ 、3.0 MPa 条件下， 反应 16.0h， 生成 (S)-2-(4-tert-Butyl-phenyl)-propionaldehyde 、 (R)-2-(4-tert-Butyl-phenyl)-propionaldehyde
  参考文献：
  名称：

  膦酰基-亚磷酰胺配体的合成及其在不对称催化中的应用

  摘要：

  通过模块化的非对映选择性过程合成了一组具有四个手性元素的磷环-磷酰胺配体。该配体被用于对映体选择性高达99％ee和周转频率高达1200 h -1的几种官能化烯烃的Rh催化不对称CC氢化反应中 ，用于Rh催化具有对映选择性的乙烯基芳烃的加氢甲酰化反应高达79％  ee的对映体，在Ir催化的不同芳基亚胺的不对称CN加氢中，对映体选择性高达ee的79％  。

  DOI：

  10.1002/cctc.201500070

文献信息

• Rhodium catalyzed asymmetric hydroformylation of vinylarenes with a diphosphite ligand forming a large chelating ring†
  作者：Zoraida Freixa、J. Carles Bayón

  DOI：10.1039/b105208j

  日期：——

  A rhodium complex containing a sixteen membered chelated diphosphite, with the appropriate combination of stereogenic centers, produces ee's above 70% in the hydroformylation of vinylarenes, while a related diastereoisomeric ligand renders very low ee's because it does not form a chelated species.

  含有十六元螯合二亚磷酸酯的铑配合物，以及适当的立体异构中心组合，在加氢甲酰化反应中产生的ee高于70％。 乙烯基芳烃，而相关的非对映异构体 配体 呈现非常低的ee，因为它不会形成螯合的物种。
• Enantioselective Hydroformylation by a Rh-Catalyst Entrapped in a Supramolecular Metallocage
  作者：Cristina García-Simón、Rafael Gramage-Doria、Saeed Raoufmoghaddam、Teodor Parella、Miquel Costas、Xavi Ribas、Joost N. H. Reek

  DOI：10.1021/ja512637k

  日期：2015.2.25

  Regio- and enantioselective hydroformylation of styrenes is attained upon embedding a chiral Rh complex in a nonchiral supramolecular cage formed from coordination-driven self-assembly of macrocyclic dipalladium complexes and tetracarboxylate zinc porphyrins. The resulting supramolecular catalyst converts styrene derivatives into aldehyde products with much higher chiral induction in comparison to the nonencapsulated Rh catalyst. Spectroscopic analysis shows that encapsulation does not change the electronic properties of the catalyst nor its first coordination sphere. Instead, enhanced enantioselectivity is rationalized by the modification of the second coordination sphere occurring upon catalyst inclusion inside the cage, being one of the few examples in achieving an enantioselective outcome via indirect through-space control of the chirality around the catalyst center. This effect resembles those taking place in enzymatic sites, where structural constraints imposed by the enzyme cavity can impart stereoselectivities that cannot be attained in bulk. These results are a showcase for the future development of asymmetric catalysis by using size-tunable supramolecular capsules.