Iminoarylphosphites with ferrocenylidene and cymantrenylidene fragments: Coordination properties and use in palladium-catalysed asymmetric allylic substitution
摘要:
Complexation of the chiral P,N-bidentate ferrocene- and cymantrene-based iminoarylphosphites with [Rh(CO)(2)O-12, [Rh(COD)(THF)(2)]BF4, [Pd(allyl)Cl](2), [Pt(allyl)Cl](4), [Pd(COD)Cl-2] and [Pt(COD)Cl-2] was found to give chelate complexes [Rh(CO)(eta(2)-PN)Cl], [Rh(COD)(eta(2)-PN)]BF4, [M(allyl)(eta(2)-PN)]BF4 (M = Pd, Pt) and cis-[M(eta(2)-PN)Cl-2)] (M = Pd, Pt), correspondingly. With the new P,N-ligands, up to 97% ee was achieved in the asymmetric Pd-catalysed alkylation of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate. In the enantioselective amination of 1,3-diphenyl-2-propenyl acetate with sodium diformylamide, up to 96% enantioselectivity was achieved. (c) 2006 Elsevier B.V. All rights reserved.
Prior studies have shown an effective way to produce diverse ligand sets for catalyst discovery is by using mixtures of monodentate forms to generate catalysts in situ. Research described here was performed to illustrate that alkene-functionalized monodentate ligands could be used in this way and in another that increases the diversity of the ligand library in an interesting way. Specifically, we hypothesized that as well as being used as monomers, these alkenes could be cross metathesized in situ immediately before the catalysis step. This combination of metathesis to form ligands in situ, then catalysis is referred to here as metacatalysis. In the event, a library of quinidine and quinine alkaloid-derived phosphites were tested as mixtures of monomers and dimers formed via metathesis in situ. The data obtained illustrated that metacatalysis can be used to identify ligands that positively and negatively modulate enantioselectivities in iridium-mediated hydrogenations of a,alpha,beta-unsaturated carboxylic acid derivatives, relative to the mixtures of the monomeric forms used. (C) 2014 Elsevier Ltd. All rights reserved.