(R)-3-acetoxy-1,3-diphenyl-1-propene | 297179-04-5

• 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: (R)-3-acetoxy-1,3-diphenyl-1-propene
• 英文别名: (-)-(R)-1,3-diphenylallyl acetate；[(E,1R)-1,3-diphenylprop-2-enyl] acetate
• CAS: 297179-04-5
• 化学式: C₁₇H₁₆O₂
• 分子量: 252.313
• InChiKey: UVJZGFKZGQSKDV-GZKZCVOOSA-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：

  (R)-3-acetoxy-1,3-diphenyl-1-propene 在 N-溴代丁二酰亚胺(NBS) 、 potassium tert-butylate 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 叔丁醇 为溶剂， 反应 59.0h， 生成 (-)-clausenamide
  参考文献：
  名称：

  （-）-Clausenamide的新型简洁合成

  摘要：

  描述了（-）-clausenamide的六步合成。将光学纯的（R，E）-1,3-二苯基烯丙醇乙酰化，然后进行Ireland-Claisen重排，得到γ，δ-不饱和酸，然后对其进行底物诱导的立体选择性溴内酯化，以提供预期的全赤道取代的溴δ-内酯。内酯的异常化学选择性氨解导致立体定向方式形成γ，δ-环氧酰胺。该中间体的碱促进环化反应和随后的Davis氧化反应完成了合成，最终产物的ee > 99％和高达34％的总产量。

  DOI：

  10.1002/cjoc.201201187
• 作为产物：
  描述：

  (±)-反式-1,3-二苯基烯丙基乙酸酯 生成 (R)-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

• New chiral phosphinooxazolidine ligands for palladium-catalyzed asymmetric allylic substitution
  作者：Myung-Jong Jin、Jung-Ae Jung、Sang-Han Kim

  DOI：10.1016/s0040-4039(99)00936-3

  日期：1999.7

  New chiral phosphinooxazolidines were prepared and examined as chiral ligands in Pd-catalyzed asymmetric allylic substitution reaction of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate or benzylamine. Enantioselectivity up to 98% was observed.

  制备了新的手性膦基恶唑烷，并在Pd催化的1,3-二苯基-2-丙烯基乙酸乙酸酯与丙二酸二甲酯或苄胺的不对称烯丙基取代反应中作为手性配体进行了研究。观察到高达98％的对映选择性。
• 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 and Unusual Regioselectivity in Palladium-Catalyzed Allylic Alkylations with a Chiral P,S Ligand
  作者：J. W. Faller、Jeremy C. Wilt、Jonathan Parr

  DOI：10.1021/ol0497382

  日期：2004.4.1

  Effective kinetic resolutions of acyclic allylic acetates and benzoates have been obtained using a palladium/(S)-BINAP(S) catalyst system. Unusually large preferences for the formation of branched alkylation products from 3-but-2-enyl and crotyl substrates have been observed.