(S)-3-acetoxy-1,3-diphenyl-1-propene | 354816-61-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: (S)-3-acetoxy-1,3-diphenyl-1-propene
• 英文别名: [(E,1S)-1,3-diphenylprop-2-enyl] acetate
• CAS: 354816-61-8
• 化学式: C₁₇H₁₆O₂
• 分子量: 252.313
• InChiKey: UVJZGFKZGQSKDV-UJGDBWEASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S)-3-acetoxy-1,3-diphenyl-1-propene 在 乙酰丙酮 作用下， 以 甲醇 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 生成 (R)-(E)-1,3-diphenyl-prop-2-en-1-ol 、 (S)-(E)-1,3-diphenylprop-2-en-1-ol
  参考文献：
  名称：

  水介导的无过渡金属Tsuji-Trost型反应

  摘要：

  在碱性水介质中用C-，O-，S-和N-亲核试剂处理1-乙酰氧基-1,3-二苯基丙烯（1）可以在没有过渡金属催化剂的情况下产生相应的取代产物。使用（S）-1和p -MeC 6 H 4 CH（OAc）CH = CHPh作为底物的机理研究提出了酯功能的BAL 1裂解，导致稳定的烯丙基碳正离子化为中间体。

  DOI：

  10.1016/j.tetlet.2003.09.038
• 作为产物：
  描述：

  (±)-反式-1,3-二苯基烯丙基乙酸酯 生成 (S)-3-acetoxy-1,3-diphenyl-1-propene
  参考文献：
  名称：

  Pd-catalyzed asymmetric synthesis of allylic tert-butyl sulfones and sulfides: Kinetic resolution of the allylic substrate by a chiral Pd-complex

  摘要：

  The acyclic and cyclic allylic tert-butyl sulfones 3, ent-3, 11a, 11b and 15a-c of 89-98% ee were synthesized in 40-92% yield by a Pd-catalyzed reaction of the respective allylic acetates and carbonates rac-1a, rac-1b, rac-10a, rac-10b and rac-14a-c with LiO(2)St-Bu in the presence of the chiral ligands 2a, ent-2b and 12. Formation of the n-butyl sulfones 13a and 13b of 95% ee was observed. Reactions of rac-1a and 1b/ent-1b with LiO(2)St-Bu in the presence of 2a and ent-2b, respectively, in THF under heterogeneous conditions were accompanied by a kinetic resolution of the allylic substrates. The faster reacting allylic substrate and the preferentially formed sulfone had the same absolute configuration. The allylic tert-butyl sulfide 17 of 92% ee was obtained in 63% yield by the Pd-catalyzed reaction of rac-1b with Me(3)SiSt-Bu in the presence of ent-2b. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(97)00601-0

文献信息

• Design of P-Chirogenic Aminophosphine–Phosphinite Ligands at Both Phosphorus Centers: Origin of Enantioselectivities in Pd-Catalyzed Allylic Reactions
  作者：Antonin Jaillet、Christophe Darcel、Jérôme Bayardon、Adrien Schlachter、Christine Salomon、Yoann Rousselin、Pierre Harvey、Sylvain Jugé

  DOI：10.1021/acs.joc.0c00536

  日期：2020.11.20

  decomplexation. Concurrently, the preparation of AMPP* ligands with a P-chirogenic phosphinite moiety was performed by N → O phosphinyl migration of aminophosphines borane by heating at 50 °C with DABCO and then reaction with chlorophosphines. AMPP* ligands were studied in palladium-catalyzed asymmetric allylic alkylations, leading to enantioselectivities from 91% (R) to 95% ee (S). X-ray crystallographic data

  我们最近获得了一项史无前例的立体定向N→O次膦基迁移工艺的专利，该工艺可将P-手性氨基膦转化为次膦酸酯。对源自麻黄碱并在氨基膦或次膦酸酯部分带有P色原中心的氨基膦次膦配体（AMPP *）进行了精细设计。具有P-生色氨基膦部分的AMPP *配体的合成是基于氧杂氮杂膦烷硼烷与有机锂试剂的公认立体反应，然后用氯膦捕获并进行硼烷分解。同时，通过将氨基膦硼烷的N→O次膦酰基迁移，通过与DABCO在50℃下加热，然后与氯膦反应，来制备具有P-生色次膦酸酯部分的AMPP *配体。R）到95％ee（S）。相关的Pd-AMPP *配合物的X射线晶体学数据和计算机建模说明了基于最稳定构象异构体与亲核试剂的MO相互作用的对映选择性的起源。
• Palladium Catalytic Species Containing Chiral Phosphites: Towards a Discrimination between Molecular and Colloidal Catalysts
  作者：Isabelle Favier、Montserrat Gómez、Guillermo Muller、M. Rosa Axet、Sergio Castillón、Carmen Claver、Susanna Jansat、Bruno Chaudret、Karine Philippot

  DOI：10.1002/adsc.200700200

  日期：2007.11.5

  Pd2 decomposes into molecular species. In addition, the high enantioselective systems, Pd1 and Pd3, are only active for a substrate containing phenyl groups. Concerning the catalytic behaviour of the corresponding molecular systems, palladium complexes coordinated to ligands 1 or 3, gave excellent asymmetric inductions, but an analogous catalyst accommodating ligand 2, was not found selective.

  钯纳米颗粒（PD1 -器Pd3通过手性二亚磷酸酯配体（稳定）1 - 3），合成并测试作为催化剂用于烯丙基烷基化反应，使用不同的底物（外消旋-我，外消旋- III和外消旋- V）。仅C-3构型不同的碳水化合物配体（1和2）导致相应纳米颗粒稳定性的显着差异：Pd1是一种坚固的催化剂，Pd2分解成分子种类。另外，对映体选择性高的系统，PD1和器Pd3，仅用于含苯基的基板活性。关于相应分子系统的催化行为，配位体1或3配位的钯配合物具有出色的不对称诱导性，但没有类似的催化剂可容纳配体2。
• Kinetic resolution of allylic esters in palladium-catalyzed asymmetric allylic alkylations using C–N bond axially chiral aminophosphine ligands
  作者：Takashi Mino、Kazuya Wakui、Shunsuke Oishi、Youtaro Hattori、Masami Sakamoto、Tsutomu Fujita

  DOI：10.1016/j.tetasy.2008.11.026

  日期：2008.12

  Chiral allylic esters, such as (R)-1,3-diphenyl-2-propenyl acetate (R)-2a, were synthesized by kinetic resolution in a palladium-catalyzed asymmetric allylic alkylation using N-aryl indoline type C–N bond axially chiral aminophosphines (S)-1 as ligands.

  手性烯丙基酯，如（- [R）-1,3-二苯基-2-丙烯基乙酸酯（- [R ）-图2a中，通过动力学拆分以合成的钯-催化的不对称烯丙基烷基化使用ñ -芳基二氢吲哚型C-N键的轴向手性氨基膦（S）-1作为配体。
• A Case for Enantioselective Allylic Alkylation Catalyzed by Palladium Nanoparticles
  作者：Susanna Jansat、Montserrat Gómez、Karine Philippot、Guillermo Muller、Ester Guiu、Carmen Claver、Sergio Castillón、Bruno Chaudret

  DOI：10.1021/ja036132k

  日期：2004.2.1

  Palladium nanoparticles (4 nm, fcc) were prepared through decomposition of [Pd2(dba)3] by H2 in the presence of a chiral xylofuranoside diphosphite. These particles catalyze the allylic alkylation of rac-3-acetoxy-1,3-diphenyl-1-propene with dimethyl malonate leading to an almost total conversion of the (R) enantiomer and almost no reaction with the (S). This gives rise to 97% ee for the alkylation

  在手性呋喃木糖苷二亚磷酸酯存在下，通过 H2 分解 [Pd2(dba)3] 制备钯纳米粒子（4 nm，fcc）。这些颗粒催化外消旋-3-乙酰氧基-1,3-二苯基-1-丙烯与丙二酸二甲酯的烯丙基烷基化，导致（R）对映体几乎完全转化，并且几乎不与（S）反应。这导致烷基化产物的 ee 为 97%，并且底物的动力学分辨率提高了约 100%。90% ee。将此行为与不同稀释度下的分子催化剂的行为进行了比较，并讨论了两种系统之间的差异。这是除众所周知的 Pt/辛可尼丁系统外，第一个显示出如此高对映选择性的胶体系统。
• Kinetic Resolution in Palladium-Catalyzed Asymmetric Allylic Alkylations by a P,O Ligand System
  作者：Scott R. Gilbertson、Ping Lan

  DOI：10.1021/ol0161256

  日期：2001.7.1

  [GRAPHICS]Through the investigation of peptide-based phosphine oxazoline ligands, a simple P,O ligand system was developed. This system provides palladium complexes that are capable of a very high degree of kinetic resolution of 1,3-diphenylprop-2-enyl acetate. The isolated palladium complex was synthesized, characterized, and determined to be an effective procatalyst.