Highly Efficient Hydrophosphonylation of Aldehydes and Unactivated Ketones Catalyzed by Methylene-Linked Pyrrolyl Rare Earth Metal Amido Complexes

• Published in: Chemistry : a European journal 2012-02, Vol.18 (9), p.2653-2659
• Main Authors: Zhou, Shuangliu, Wu, Zhangshuan, Rong, Jiewei, Wang, Shaowu, Yang, Gaosheng, Zhu, Xiancui, Zhang, Lijun
• Format: Article
• Language: English
• Subjects: Aldehydes; Aldehydes - chemistry; Amides - chemistry; carbonyl compounds; Catalysis; Catalysts; Catalytic activity; Chemistry; Coordination compounds; Crystallography, X-Ray; Earth; homogeneous catalysis; hydrophosphonylation; Ketones; Ketones - chemistry; Ligands; Magnetic Resonance Spectroscopy; Metals, Rare Earth - chemistry; Models, Molecular; organometallic compounds; Organometallic Compounds - chemistry; Organophosphonates - chemistry; Phosphonates; Rare earth metals; rare earths; Stereoisomerism; Trace elements
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201102207

A series of rare earth metal amido complexes bearing methylene‐linked pyrrolyl‐amido ligands were prepared through silylamine elimination reactions and displayed high catalytic activities in hydrophosphonylations of aldehydes and unactivated ketones under solvent‐free conditions for liquid substrates. Treatment of [(Me3Si)2N]3Ln(μ‐Cl)Li(THF)3 with 2‐(2,6‐Me2C6H3NHCH2)C4H3NH (1, 1 equiv) in toluene afforded the corresponding trivalent rare earth metal amides of formula {(μ‐η5:η1):η1‐2‐[(2,6‐Me2C6H3)NCH2](C4H3N)LnN(SiMe3)2}2 [Ln=Y (2), Nd (3), Sm (4), Dy (5), Yb (6)] in moderate to good yields. All compounds were fully characterized by spectroscopic methods and elemental analyses. The yttrium complex was also characterized by 1H NMR spectroscopic analyses. The structures of complexes 2, 3, 4, and 6 were determined by single‐crystal X‐ray analyses. Study of the catalytic activities of the complexes showed that these rare earth metal amido complexes were excellent catalysts for hydrophosphonylations of aldehydes and unactivated ketones. The catalyzed reactions between diethyl phosphite and aldehydes in the presence of the rare earth metal amido complexes (0.1 mol %) afforded the products in high yields (up to 99 %) at room temperature in short times of 5 to 10 min. Furthermore, the catalytic addition of diethyl phosphite to unactivated ketones also afforded the products in high yields of up to 99 % with employment of low loadings (0.1 to 0.5 mol %) of the rare earth metal amido complexes at room temperature in short times of 20 min. The system works well for a wide range of unactivated aliphatic, aromatic or heteroaromatic ketones, especially for substituted benzophenones, giving the corresponding α‐hydroxy diaryl phosphonates in moderate to high yields. Lanthanide catalysts: Highly efficient hydrophosphonylations of aldehydes and unactivated ketones were catalyzed by low loadings of dinuclear rare earth metal amido complexes bearing methylene‐linked pyrrolylamido ligands (see scheme). The system works well for a wide range of aldehydes and ketones and, notably, substituted benzophenones, giving the corresponding α‐hydroxy diaryl phosphonates in moderate to high yields.