Mild and Efficient Heterogeneous Hydrogenation of Nitroarenes Facilitated by a Pyrolytically Activated Dinuclear Ni(II)-Ce(III) Diimine Complex.

We communicate the assembly of a solid, Ce-promoted Ni-based composite that was applied as catalyst for the hydrogenation of nitroarenes to afford the corresponding organic amines. The catalytically active material described herein was obtained through pyrolysis of a SiO-pellet-supported bimetallic Ni-Ce complex that was readily synthesized prior to use from a MeO-functionalized salen congener, Ni(OAc)·4 HO, and Ce(NO)·6 HO. Rewardingly, the requisite ligand for the pertinent solution phase precursor was accessible upon straightforward and time-saving imine condensation of -vanillin with 1,3-diamino-2,2'-dimethylpropane.

Enantioselective Bifunctional Ammonium Salt-Catalyzed Syntheses of 3-CFS-, 3-RS-, and 3-F-Substituted Isoindolinones.

We herein report the ammonium salt-catalyzed synthesis of chiral 3,3-disubstituted isoindolinones bearing a heteroatom functionality in the 3-position. A broad variety of differently substituted CFS- and RS-derivatives were obtained with often high enantioselectivities when using Maruoka's bifunctional chiral ammonium salt catalyst. In addition, a first proof-of-concept for the racemic synthesis of the analogous F-containing products was obtained as well, giving access to one of the rare examples of a fairly stable α-F-α-amino acid derivative.

Synthesis of α-CF-proline derivatives by means of a formal (3 + 2)-cyclisation between trifluoropyruvate imines and Michael acceptors.

We herein report the first formal (3 + 2)-cyclisation between 3,3,3-trifluoropyruvate-derived imines and indandione-based Michael acceptors. This reaction gives access to a novel class of spirocyclic α-CF3-α-proline derivatives with complete control of the diastereoselectivity under phase transfer-catalysed reaction conditions.

Asymmetric phase-transfer catalysed β-addition of isoxazolidin-5-ones to MBH carbonates.

A novel high yielding, and diastereoselective protocol for the synthesis of α-allylated highly functionalised β-amino acid derivatives by adding isoxazolidin-5-ones to MBH carbonates under asymmetric phase-transfer catalysis has been developed.

Synthetic strategies to bicyclic tetraphosphanes using P1, P2 and P4 building blocks.

Different reactions of Mes* substituted phosphanes (Mes* = 2,4,6-tri-tert-butylphenyl) led to the formation of the bicyclic tetraphosphane Mes*P4Mes* (5) and its unknown Lewis acid adduct 5·GaCl3. In this context, the endo-exo isomer of 5 was fully characterized for the first time. The synthesis was achieved by reactions involving "self-assembly" of the P4 scaffold from P1 building blocks (i.

Low-Temperature Isolation of the Bicyclic Phosphinophosphonium Salt [Mes*2P4Cl][GaCl4].

The reaction of [ClP(μ-PMes*)]2 (1) with the Lewis acid GaCl3 yielded a hitherto unknown tetraphosphabicyclo[1.1.0]butan-2-ium salt, [Mes*P4(Cl)Mes*][GaCl4] (3[GaCl4]), which incorporates a positively charged phosphonium center within its bicyclic P4 scaffold.