WalPhos配体/铑配合物对β,γ-不饱和膦酸酯的不对称催化氢化

doi:10.3724/SP.J.1095.2014.30194

摘要/Abstract

摘要： 用手性配体(Rc,Sp)-WalPhos与铑形成的配合物为催化剂，在1.0 MPa的氢气压力、二氯甲烷溶剂中以及室温的反应条件下，对β-取代-β,γ-不饱和膦酸酯底物进行不对称催化氢化，合成了具有β-手性中心的手性膦酸酯类化合物，所有考察的底物均可完全转化，最高获得了87%的ee值。

关键词: beta-取代-beta,gamma-不饱和膦酸酯, 不对称催化氢化, 铑, 手性beta-芳基取代丙基膦酸酯

Key words: beta-substituted-beta,gamma-unsaturated phosphonates, asymmetric catalytic hydrogenation, rhodium, chiral beta-aryl-substituted propylphosphonates

中图分类号:

O643.3

段正超, 王联芝, 左晓宇, 屈桃李, 胡向平, 郑卓. WalPhos配体/铑配合物对β,γ-不饱和膦酸酯的不对称催化氢化[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30194.

DUAN Zhengchao1*, WANG Lianzhi1, ZUO Xiaoyu1, QU Taoli1, HU Xiangping2*, ZHENG Zhu2. Rh-catalyzed Asymmetric Hydrogenation of β,γ-Unsaturated Phosphonates with WalPhos Ligands[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30194.

参考文献

[1] Hilderbrand R L. The Role of Phosphonates in Living Systems[M]. CRC Press,Boca Raton,1983.

[2] Bellucci C,Gualtieri F,Scapecchi S,et al. Negative Inotropic and Calcium-antagonist Activity of Alkil and Arylalkyl Phosphonates[J]. II Farmaco,1989,44:1167-1191.

[3] Kafarski P,Lejczak B. Biological Activity of Aminophosphonic Acids[J]. Phosphorus Sulfur Silicon Relat Elem,1991,63:193-215.

[4] Savignac P,Iorga B. Morden Phosphonate Chemistry[M]. CRC Press,Boca Raton,2003.

[5] Hayashi T,Senda T,Takaya Y,et al. Rhodium-Catalyzed Asymmetric 1,4-Addition to 1-Alkenylphosphonates[J]. J Am Chem Soc,1999,121:11591-11592.

[6] Duan Z C,Hu X P,Wang D Y,et al. Cu-Catalyzed Asymmetric Conjugate Reduction of β-Substituted α,β-Unsaturated Phosphonates:an Efficient Synthesis of Optically Active β-Stereogenic Alkylphosphonates[J]. Tetrahedron Lett,2009,50:6720-6722.

[7] de Vries J G. The Handbook of Homogeneous Hydrogenation[M]. Wiley-VCH:Weinheim,Germany,2007:1-3.

[8] Duan Z C,Hu X P,Wang D Y,et al. Enantioselective Synthesis of Optically Active Alkanephosphonates via Rhodium-Catalyzed Asymmetric Hydrogenation of beta-Substituted alpha,beta-Unsaturated Phosphonates with Ferrocene-based Monophosphoramidite Ligands[J]. Adv Synth Catal,2008,350:1979-1983.

[9] Duan Z C,Hu X P,Zhang C,et al. Highly Enantioselective Rh-Catalyzed Hydrogenation of β,γ-Unsaturated Phosphonates with Chiral Ferrocene-Based Monophosphoramidite Ligands[J]. J Org Chem,2009,74:9191-9194.

[10] Luo L B,Wang D Y,Zhou X M,et al. Asymmetric Synthesis of 2-Alkyl-3-Phosphonopropanoic Acid Derivatives via Rh-Catalyzed Asymmetric Hydrogenation[J]. Tetrahedron:Asymm,2011,22:2117-2123.

[11] Duan Z C,Wang L Z,Song X J,et al. Enantioselective Synthesis of Optically Active Alkylphosphonates via Rh-Catalyzed Asymmetric Hydrogenation of β-Substituted α,β-Unsaturated Phosphonates[J]. Tetrahedron:Asymm,2012,23:508-514.