Platinum-Catalyzed Regio- and Enantioselective Diboration of Unactivated Alkenes with (pin)B-B(dan).

Asymmetric diboration of terminal alkenes is well established, and subsequent selective functionalization of the less hindered primary boronic ester is commonly achieved. Conversely, selective functionalization of the sterically less accessible secondary boronic ester remains challenging. An alternative way to control chemoselective functionalization of bis(boron) compounds is by engendering different Lewis acidity to the two boryl moieties, since reactivity would then be dictated by Lewis acidity instead of sterics.

Difluorinated thromboxane A reveals crosstalk between platelet activatory and inhibitory pathways by targeting both the TP and IP receptors.

Background And Purpose: Thromboxane A (TXA) is a prostanoid produced during platelet activaton, important in enhancing platelet reactivity by activation of TP receptors. However, due to the short half-life, studying TXA signalling is challenging. To enhance our understanding of TP receptor-mediated platelet biology, we therefore synthesised mono and difluorinated TXA analogues and explored their pharmacology on heterologous and endogenously expressed TP receptor function.

Ruthenium-Catalyzed Dual Dehydrogenative Silylation of C(sp)-H Bonds: Access to Diverse Silicon-Centered Spirocycles.

We report herein a pincer Ru-catalyzed dual intramolecular dehydrogenative silylation of primary C(sp)-H bonds. The reaction features high efficiency, scalability, and good functional group tolerance, allowing a facile and atom-economical access to structurally diverse silicon-centered spirocycles, including unprecedented oxa-spirosilabiindanes and aza-spirosilabiindanes.

Defunctionalisation catalysed by boron Lewis acids.

Selective defunctionalisation of organic molecules to valuable intermediates is a fundamentally important transformation in organic synthesis. Despite the advances made in efficient and selective defunctionalisation using transition-metal catalysis, the cost, toxicity, and non-renewable properties limit its application in industrial manufacturing processes. In this regard, boron Lewis acid catalysis has emerged as a powerful tool for the cleavage of carbon-heteroatom bonds.

Consecutive β,β'-Selective C(sp )-H Silylation of Tertiary Amines with Dihydrosilanes Catalyzed by B(C F ).

Tris(pentafluorophenyl)borane has been found to catalyze the two-fold C(sp )-H silylation of various trialkylamine derivatives with dihydrosilanes, furnishing the corresponding 4-silapiperidines in decent yields. The multi-step reaction cascade involves amine-to-enamine dehydrogenation at two alkyl residues and two electrophilic silylation reactions of those enamines, one inter- and one intramolecular.

Ruthenium-Catalyzed Hydrodefluorination with Silane as the Directing and Reducing Group.

We describe herein an efficient and selective Ru-catalyzed intramolecular HDF directed by a silyl group, which is readily installed, and removable and transformable following the HDF reaction. The hydrosilyl group in polyfluoroaryl silane acts not only as the directing group but also as the internal reductant, enabling precise control of the -selectivity and avoiding overdefluorination. Mechanistic studies reveal a plausible catalytic cycle involving a Ru(IV)-aryne intermediate.

The Cyclohexa-2,5-dienyl Group as a Placeholder for Hydrogen: Organocatalytic Michael Addition of an Acetaldehyde Surrogate.

An aldehyde with a cyclohexa-2,5-dienyl group in the α-position is introduced as a storable surrogate of highly reactive acetaldehyde. The cyclohexa-2,5-dienyl unit is compatible with an enantioselective Michael addition to nitroalkenes promoted by a Hayashi-Jørgensen catalyst and can be removed by a boron Lewis acid mediated C-C bond cleavage. The robust two-step sequence does not require a large excess of the aldehyde component that is typically needed when directly using acetaldehyde.

Reductive Deamination with Hydrosilanes Catalyzed by B(C F ).

The strong boron Lewis acid tris(pentafluorophenyl)borane B(C F ) is known to catalyze the dehydrogenative coupling of certain amines and hydrosilanes at elevated temperatures. At higher temperature, the dehydrogenation pathway competes with cleavage of the C-N bond and defunctionalization is obtained. This can be turned into a useful methodology for the transition-metal-free reductive deamination of a broad range of amines as well as heterocumulenes such as an isocyanate and an isothiocyanate.

A BEt-Base Catalyst for Amide Reduction with Silane.

Reported herein is the development of a simple but practical catalytic system for the selective reduction of amides with hydrosilane or hydrosiloxane. Low-cost and readily available triethylborane (1.0 M in THF), in combination with a catalytic amount of an alkali metal base, was found to catalyze the reduction of all three amide classes (tertiary, secondary, and primary amides) to form amines under mild conditions.

Ruthenium-Catalyzed Site-Selective Intramolecular Silylation of Primary C-H Bonds for Synthesis of Sila-Heterocycles.

Incorporating the silicon element into bioactive organic molecules has received increasing attention in medicinal chemistry. Moreover, organosilanes are valuable synthetic intermediates for fine chemicals and materials. Transition metal-catalyzed C-H silylation has become an important strategy for C-Si bond formations.

A Pincer Ruthenium Complex for Regioselective C-H Silylation of Heteroarenes.

A pincer Ru(II) catalyst for the highly efficient undirected silylation of O- and S-heteroarenes with (TMSO)MeSiH and EtSiH is described, producing heteroarylsilanes with exclusive C2-regioselectivity, good functional-group tolerance, and high turnover numbers (up to 1960). The synthetic utility of the silylated products is demonstrated by Pd-catalyzed Hiyama-Denmark cross-coupling under mild conditions. One-pot, two-step silylation and coupling procedures have been also developed.

A General and mild catalytic α-alkylation of unactivated esters using alcohols.

Catalytic α-alkylation of esters with primary alcohols is a desirable process because it uses low-toxicity agents and generates water as the by-product. Reported herein is a NCP pincer/Ir catalyst which is highly efficient for α-alkylation of a broad scope of unactivated esters under mild reaction conditions. For the first time, alcohols alkylate unactivated α-substituted acyclic esters, lactones, and even methyl and ethyl acetates.