Selective Reduction of Secondary Amides to Imines Catalysed by Schwartz's Reagent.

The partial reduction of amides is a challenging transformation that must overcome the intrinsic stability of the amide bond and exhibit high chemoselective control to avoid overreduction to amine products. To address this challenge, we describe a zirconium-catalysed synthesis of imines by the reductive deoxygenation of secondary amides. This reaction exploits the excellent chemoselectivity of Schwartz's reagent (Cp2 Zr(H)Cl) and utilises (EtO)3 SiH as a mild stoichiometric reductant to enable catalyst turnover. The reaction generally proceeds with high yields (19 examples, 51 to 95 % yield) and tolerates a variety of functional groups (alkene, ester, nitro, etc.). Stoichiometric mechanistic investigations suggest the regeneration of the active [Zr]-H catalyst is achieved through the metathesis of Si-H and Zr-OR σ-bonds.

Arylboronic Acid Catalyzed C-Alkylation and Allylation Reactions Using Benzylic Alcohols.

The arylboronic acid catalyzed dehydrative C-alkylation of 1,3-diketones and 1,3-ketoesters using secondary benzylic alcohols as the electrophile is reported, forming new C-C bonds (19 examples, up to 98% yield) with the release of water as the only byproduct. The process is also applicable to the allylation of benzylic alcohols using allyltrimethylsilane as the nucleophile (12 examples, up to 96% yield).

Synthesis and structures of anionic rhenium polyhydride complexes of boron-hydride ligands and their application in catalysis.

The rhenium complex, [K(DME)(18-c-6)][ReH4(Bpin)(η2-HBpin)(κ2-H2Bpin)] 1, comprising hydride and boron ligands only, has been synthesized by exhaustive deoxygenation of the commercially available perrhenate anion (ReO4 -) with pinacol borane (HBpin). The structure of 1 was analysed by X-ray crystallography, NMR spectroscopy, and DFT calculations. While no hydrides were located in the X-ray crystal structure, it revealed a trigonal arrangement of pinacol boron ligands. Variable-temperature NMR spectroscopy supported the presence of seven hydride ligands but further insight was hindered by the fluxionality of both hydride and boron ligands at low temperature. Further evaluation of the structure by Ab Initio Random Structure Searching (AIRSS) identified the presence of hydride, boryl, σ-borane, and dihydroborate ligands. This complex, either isolated or prepared in situ, is a catalyst for the 1,4-hydroboration of N-heteroaromatic substrates under simple operating procedures. It also acts as a reagent for the stoichiometric C-H borylation of toluene, displaying high meta regioselectivity in the borylated products. Reaction of 1 with 9-BBN resulted in HBpin substitution to form the new anionic tetra(dihydroborate) complex [K(DME)(18-c-6)][Re(κ2-H-9-BBN)4] 4 for which the hydride positions were clearly identified by X-ray crystallography. The method used to generate these isolable yet reactive boron-hydride complexes is direct and straightforward and has potential utility for the exploitation of other metal oxo compounds in operationally simple catalytic reactions.

Recent Advances in the Deoxydehydration of Vicinal Diols and Polyols.

Deoxydehydration (DODH) is one of the most promising tools to reduce the oxygen content of biomass (sugars and polyols) and provide analogues of platform chemicals that are derived from fossil resources. This reaction converts a vicinal diol into an alkene and is typically catalyzed by high-oxidation-state metal-oxo compounds in the presence of a stoichiometric reductant, with examples of both homogeneous and heterogeneous systems. This minireview will highlight the developments in this field over the past 5 years and focus on efforts to solve the problems that currently prevent DODH being performed on a commercial scale, including the nature of the reductant, substrate scope and selectivity, and catalyst recovery and expense.

Aryl Boronic Acid Catalysed Dehydrative Substitution of Benzylic Alcohols for C-O Bond Formation.

A combination of pentafluorophenylboronic acid and oxalic acid catalyses the dehydrative substitution of benzylic alcohols with a second alcohol to form new C-O bonds. This method has been applied to the intermolecular substitution of benzylic alcohols to form symmetrical ethers, intramolecular cyclisations of diols to form aryl-substituted tetrahydrofuran and tetrahydropyran derivatives, and intermolecular crossed-etherification reactions between two different alcohols. Mechanistic control experiments have identified a potential catalytic intermediate formed between the aryl boronic acid and oxalic acid.

Exploiting the Bis-Nucleophilicity of α-Aminoboronates: Copper-Catalyzed, Intramolecular Aminoalkylations of Bromobenzoyl Chlorides.

α-Aminoboronate salts are interesting examples of heteroatomic species containing adjacent nucleophilic centers. We have developed an acylation/arylation reaction using 2-bromobenzoyl chlorides as bis-electrophiles that harnesses the nucleophilicity of both positions, leading to isoindolinones. The reactions proceed under mild conditions via an intramolecular, Cu-catalyzed sp(3)-sp(2) coupling, giving products in up to 95% yield. These conditions enable arylation of α,α-disubstituted aminoboronates, which are difficult to accomplish using methods based on less abundant and more expensive transition metals.

Catalytic reductive N-alkylation of amines using carboxylic acids.

We report a catalytic reductive alkylation reaction of primary or secondary amines with carboxylic acids. The two-phase process involves silane mediated direct amidation followed by catalytic reduction.