有机化学 ›› 2016, Vol. 36 ›› Issue (12): 2912-2919.DOI: 10.6023/cjoc201604022 上一篇    下一篇

研究论文

C3对称的新型单齿亚磷酸酯配体在不对称氢甲酰化和1,4-共轭加成中的应用研究

邢爱萍a, 田密a,b, 王来来a   

  1. a 中国科学院兰州化学物理研究所 羰基合成与选择氧化国家重点实验室 兰州 730000;
    b 中国科学院大学 北京 100039
  • 收稿日期:2016-04-11 修回日期:2016-06-29 发布日期:2016-08-22
  • 通讯作者: 王来来 E-mail:wll@licp.cas.cn
  • 基金资助:

    国家自然科学基金(Nos. 20773147,21073211,21174155)资助项目.

Novel Chiral C3-Symmetric Monophosphite Ligands: Synthsis and Catalytic Performance in Asymmetric Hydroformylation and 1,4-Conjugate Addition

Xing Aipinga, Tian Mia,b, Wang Lailaia   

  1. a State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000;
    b Graduate University of Chinese Academy of Sciences, Beijing, 100039
  • Received:2016-04-11 Revised:2016-06-29 Published:2016-08-22
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 20773147, 21073211, 21174155).

以(R)或(S)-H8-BINOL为配体骨架,合成具有螺旋结构C3对称的六个新型单齿亚磷酸酯配体,并将它们首次成功应用于Rh(acac)(CO)2催化苯乙烯的不对称氢甲酰化,和Cu(OTf)2催化二乙基锌对链烯酮的不对称1,4-共轭加成反应研究中.在铑催化苯乙烯的不对称氢甲酰化反应中,螺旋结构C3对称的单齿亚磷酸酯配体给出高的催化活性(转化率93%)和支链醛/直链醛区域选择性(b/n=95/5),和较低的对映选择性[28% eeR)].在铜催化二乙基锌对链烯酮的不对称1,4-共轭加成反应中,以查尔酮为底物筛选配体,优化反应条件;在优化的反应条件下,考察11种不同结构链状烯酮底物对反应的适应性;以Cu(OTf)2作为催化剂前体,乙醚为溶剂,在-20℃,配体(R)-3中大位阻金刚烷基和(R)-H8-联萘基团之间的空间结构匹配是获得98%分离产率和72%(R)对映选择性的关键因素,产物绝对构型主要由配体结构中H8-联萘基团的构型决定.研究结果证明C3对称的新型单齿亚磷酸酯配体在不对称氢甲酰化和1,4-共轭加成反应中具有应用潜力.

关键词: 不对称氢甲酰化和1,4-共轭加成, 单齿亚磷酸酯配体, 铑和铜的络合物, 苯乙烯和链烯酮, 活性和对映选择性

A family of the novel chiral helical C3-symmetric monophosphite ligands has been synthesized from axially chiral (R)-or (S)-H8-BINOL and PCl3. The performance of these ligands in asymmetric catalysis was evaluated by the Rh-catalyzed asymmetric hydroformylation of styrene, and the Cu-catalyzed asymmetric 1,4-conjugate addition of diethylzinc to acyclic enones. The catalytic hydroformylation of styrene gave rather high conversion (93%), high regioselectivity (b/n=95/5) and low enantioselectivity[28% ee (R)] using ligand (R)-2 in tetrahydrofuran at room temperature. Under the optimal 1,4-conjugate addition of ZnEt2 to chalcone 3a conditions, eleven acyclic enones 4a~4k were all converted smoothly to the 1,4-adducts with high enantiomeric excess. Using Cu(OTf)2 as catalyst precursor and Et2O as solvent at -20℃, the structure of ligand (R)-3 comprising a partially hydrogenated 2,2'-(1,1'-binaphthyl)-phosphite scaffold and an adamantyl moiety was key factor in improving catalytic activity and the enantioselectivity with up to 98% yield and 72% ee (R). The sense of enantiodiscrimination of the reaction was controlled by the configuration of the diaryl phosphite moieties.

Key words: asymmetric hydroformylation and 1,4-conjugate addition, monophosphite, the Rh- and Cu-complexes, styrene and acyclic enones, catalytic activity and enantioselectivity