Samarium-Catalyzed Diastereoselective Double Addition of Phenylphosphine to Imines and Mechanistic Studies by DFT Calculations

bibtex: ISI:000400097100003 bibtex\location:'POSTFACH 101161, 69451 WEINHEIM, GERMANY',publisher:'WILEY-V C H VERLAG GMBH',type:'Article',affiliation:'Cui, CM (Reprint Author), Nankai Univ, State Key Lab Elementoorgan Chem, Collaborat Innovat Ctr Chem Sci & Engn, Tianjin 300071, Peoples R China. Maron, L (Reprint Author), Univ Toulouse, LPCNO, CNRS, INSA,UPS,UMR 5215, 135 Ave Rangueil, F-31077 Toulouse, France. Li, Jianfeng; Song, Changhong; Liu, Jinxi; Fan, Guilan; Cui, Chunming, Nankai Univ, State Key Lab Elementoorgan Chem, Collaborat Innovat Ctr Chem Sci & Engn, Tianjin 300071, Peoples R China. Lamsfus, Carlos Alvarez; Maron, Laurent, Univ Toulouse, LPCNO, CNRS, INSA,UPS,UMR 5215, 135 Ave Rangueil, F-31077 Toulouse, France.','author-email':'[email protected] [email protected]',da:'2018-12-05','doc-delivery-number':'ET2JI',eissn:'1867-3899','funding-acknowledgement':'National Natural Science Foundation of China [21390401]; Humboldt Foundation; Chinese Academy of Sciences','funding-text':'We are grateful to the National Natural Science Foundation of China (21390401) for financial support. L.M. is a member of the Institut Universitaire de France. The Humboldt Foundation and the Chinese Academy of Sciences are acknowledged for financial support of this work. L.M. and C.A.L. are grateful to CalMip for the generous grant of computing time.','journal-iso':'ChemCatChem','keywords-plus':'H BOND ADDITION; AMINOPHOSPHINE LIGANDS; ASYMMETRIC ADDITION; CHIRAL 3,4-DIAZAPHOSPHOLANES; ALPHA-AMINOPHOSPHINES; EFFICIENT SYNTHESIS; METAL-COMPLEXES; HYDROPHOSPHINATION; ALKENES; CARBODIIMIDES','number-of-cited-references':'48','orcid-numbers':'Alvarez Lamsfus, Carlos/0000-0002-4442-7052','research-areas':'Chemistry','times-cited':'2','unique-id':'ISI:000400097100003','usage-count-last-180-days':'4','usage-count-since-2013':'13','web-of-science-categories':'Chemistry, Physical'\The catalytic hydrophosphination of imines represents the most straightforward and atom-economical strategy for the preparation of alpha-aminophosphines, which are useful as biologically active molecules and ligands for catalysis. The first catalytic protocol for the rapid and high-yielding hydrophosphination of common imines enabled by an ene-diamido samarium methoxide catalyst was developed. The reaction allowed the efficient and diastereoselective synthesis of various bis(alpha-amino)phosphines through the double addition of PhPH2 to common imines. The catalytic reaction has a relatively wide substrate scope and offers high diastereoselectivities (up to 99: 1 dr for meso products) and high yields (up to 97%). DFT calculations disclosed an inner-sphere mechanism involving unprecedented activation of a Sm-O bond by a phosphine and stabilization of the addition intermediates by the metal center

Amino-phosphanes in Rh(I)-catalyzed hydroformylation: hemilabile behavior of P,N ligands under high CO pressure and catalytic properties

International audienceThe catalytic properties of rhodium complexes containing the α-, β-, or γ-amino-phosphane ligands Ph2PCH2NEt2 (α-P,N-1), Ph2PCH(Ar)NHPh [α-P,N-2; Ar = η6(o-C6H4Cl)Cr(CO)3], Ph2PCH2NPh2 (α-P,N-3), Ph2PCH2CH(Ph)NHPh (β-P,N), Ph2PCH2(o-C6H4–NMe2) (γ-P,N-1), Ph2PCH(o-C6H4–CH2NHPh) (γ-P,N-2), and the α,β-diamino-phosphane ligand Et2NCH2P(Ph)CH2CH(Ph)NHPh (α,β-N,P,N), in styrene hydroformylation have been examined. The results show that the activity increases when the number of backbone carbon atoms linking P and N decreases from 3 to 1. IR and 31P HPNMR studies in solution show that all P,N ligands adopt exclusively a κ1-P coordination mode in rhodium chloride carbonyl complexes under high CO pressure. In the solid state a κ1-P-α-amino-phosphane coordination has been ascertained by X-ray methods in trans-[RhCl(CO)(γ-P,N-1)2]. In contrast, an equilibrium between the κ2-P,N and κ1-P-coordination modes has been observed as a function of the CO pressure for the complex containing the β-P,N ligand. The basicity of the dangling amino group also plays an important role on the catalytic activity and a mechanism involving the nitrogen function in the catalytic cycle is proposed