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

doi:10.6023/cjoc201604022

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

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 Aiping^a, Tian Mi^a,b, Wang Lailai^a

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).

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摘要/Abstract

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% ee （R）].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

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邢爱萍, 田密, 王来来. 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[J]. 有机化学, 2016, 36(12): 2912-2919.

Xing Aiping, Tian Mi, Wang Lailai. Novel Chiral C3-Symmetric Monophosphite Ligands: Synthsis and Catalytic Performance in Asymmetric Hydroformylation and 1,4-Conjugate Addition[J]. Chin. J. Org. Chem., 2016, 36(12): 2912-2919.

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[1] Reetz, M. T.; Guo, H.; Ma, J.-A.; Goddard, R.; Mynott, R. J. J. Am. Chem. Soc. 2009, 131, 4136.
[2] Carrilho, R. M. B.; Costa, G. N.; Neves, Â. C. B.; Pereira, M. M.; Grabulosa, A.; Bayón, J. C.; Rocamora, M.; Muller, G. Eur. J. Inorg. Chem. 2014, 1034.
[3] Gual, A.; Godard, C.; Castillón, S.; Claver, C. Tetrahedron:Asymmetry 2010, 21, 1135.
[4] Hou, C.; Liu, X.; Xia, Y.; Hu, X. Chin. J. Org. Chem. 2012, 32, 2239(in Chinese).(侯传金, 刘小宁, 夏英, 胡向平, 有机化学, 2012, 32, 2239.)
[5] Franke, R.; Selent, D.; Borner, A. Chem. Rev. 2012, 112, 5675.
[6] Rossiter, B. E.; Swingle, N. M. Chem. Rev. 1992, 92, 771.
[7] Krause, N. Angew. Chem., Int. Ed. 1998, 37, 283.
[8] Krause, N.; Hoffmann-Röder, A. Synthesis 2001, 0171.
[9] Alexakis, A.; Benhaim, C. Eur. J. Org. Chem. 2002, 3221.
[10] Hayashi, T.; Yamasaki, K. Chem. Rev. 2003, 103, 2829.
[11] Woodward, S. Chem. Soc. Rev. 2000, 29, 393.
[12] Alexakis, A.; Bäckvall, J. E.; Krause, N.; Pàmies, O.; Diéguez, M. Chem. Rev. 2008, 108, 2796.
[13] Choi, Y. H.; Choi, J. Y.; Yang, H. Y.; Kim, Y. H. Tetrahedron:Asymmetry 2002, 13, 801.
[14] Cesati; de Armas, J.; Hoveyda, A. H. J. Am. Chem. Soc. 2004, 126, 96.
[15] Degrado, S. J.; Mizutani, H.; Hoveyda, A. H. J. Am. Chem. Soc. 2001, 123, 755.
[16] Arnold, L. A.; Naasz, R.; Minnaard, A. J.; Feringa, B. L. J. Org. Chem. 2002, 67, 7244.
[17] Dijk, E. W.; Panella, L.; Pinho, P.; Naasz, R.; Meetsma, A.; Minnaard, A. J.; Feringa, B. L. Tetrahedron 2004, 60, 9687.
[18] Polet, D.; Alexakis, A. Tetrahedron Lett. 2005, 46, 1529.
[19] Alexakis, A.; Frutos, J.; Mangeney, P. Tetrahedron:Asymmetry 1993, 4, 2427.
[20] Mata, Y.; Diéguez, M.; Pàmies, O.; Biswas, K.; Woodward, S. Tetrahedron:Asymmetry 2007, 18, 1613.
[21] Diéguez, M.; Ruiz, A.; Claver, C. Tetrahedron:Asymmetry 2001, 12, 2861.
[22] Zhang, Z. F.; Xie, F.; Yang, B.; Yu, H.; Zhang, W. B. Chin. J. Org. Chem. 2011, 31, 429(in Chinese).(张振锋, 谢芳, 杨波, 余焓, 张万斌, 有机化学, 2011, 31, 429.)
[23] Liang; Au-Yeung, T. T. L.; Chan, A. S. C. Org. Lett. 2002, 4, 3799.
[24] Wang, L.; Li, Y.-M.; Yip, C.-W.; Qiu, L.; Zhou, Z.; Chan, A. S. C. Adv. Synth. Catal. 2004, 346, 947.
[25] Zhao, Q.-L.; Wang, L.-L. Tetrahedron:Asymmetry 2011, 22, 1885.
[26] Wan, H.; Hu, Y.; Liang, Y.; Gao, S.; Wang, J.; Zheng, Z.; Hu, X. J. Org. Chem. 2003, 68, 8277.
[27] Hu, Y.; Liang, X.; Wang, J.; Zheng, Z.; Hu, X. Tetrahedron:Asymmetry 2003, 14, 3907.
[28] Li, Z. G. Preparation of Organic Intermediates, 2nd ed., Chemical Industry Press, Beijing, 2010, pp. 48~73(in Chinese).(李在国, 有机中间体制备(第二版), 化学工业出版社,北京, 2010, pp. 48~73.)

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

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

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