David J. Jones

University College Cork | UCC · Department of Chemistry

A robust methodology for the synthesis of phosphorothioates, phosphinothioates and phosphonothioates, including those bearing low molecular weight S‐alkyl side‐chains, is presented. Application of the “caesium effect” in conjunction with the disulfide 3,3’‐dithiobis(propionitrile), which acts as a shelf‐stable sulfur source, avoids recourse to malo...

Phosphorothioates, phosphonothioates, phosphinothioates and phosphonodithioates are organophosphorus compounds with widespread application, especially in the fields of agrochemicals, medicinal chemistry and materials chemistry. Herein, we review modern methods for the construction of the phosphorus‐sulfur bonds in these important functional groups....

A biomimetic synthetic strategy has resulted in a two‐step total synthesis of (±)‐ulodione A and the prediction of two potential natural products, (±)‐ulodiones C and D. This work was guided by computational investigations into the selectivity of a proposed biosynthetic Diels–Alder dimerization, which was then utilized in the chemical synthesis. Th...

One-pot processes which facilitate a number of tandem reactions, represent an environmentally friendly approach to building molecular complexity. In addition, there are significant cost and time saving benefits. However, unearthing multiple reactions that display substrate, reagent and solvent compatibility across two or more reactions, is not stra...

Enantioconvergent reactions are pre-eminent in contemporary asymmetric synthesis as they convert both enantiomers of a racemic starting material into a single enantioenriched product, thus avoiding the maximum 50% yield associated with resolutions. All currently known enantioconvergent processes necessitate the loss or partial loss of the racemic s...

The introduction of added ‘3‐dimensionality’ through late‐stage functionalisation of extended (hetero)aromatic systems is a powerful synthetic approach. The abundance of starting materials and cross‐coupling methodologies to access the precursors allows for highly diverse products. Subsequent selective partial reduction can alter the core structure...

Dibenzofuran and its derivatives are ubiquitous and important medicinal and natural products. Many contain electron‐rich aryl rings. Forming the key intramolecular Ar−Ar bond using traditional cross‐coupling is difficult. The C−H functionalisation (C−H activation) approach is, in principle, far more useful. However, we previously found that the wel...

The stereoselective synthesis of chiral molecules in enantioenriched form-i.e., asymmetric synthesis-underpins many fields of pure and applied science. 1,2 Enantioconvergent reactions are preeminent in contemporary asymmetric synthesis as they convert both enantiomers of a racemic starting material into a single enantioenriched product, thus avoidi...

A biomimetic synthetic strategy has resulted in a 2‐step total synthesis of (±)‐ulodione A and the prediction of two potential natural products, (±)‐ulodiones C and D. This work was guided by computational investigations into the selectivity of a proposed biosynthetic Diels–Alder dimerization, which was then utilized in the chemical synthesis. This...

A biomimetic synthetic strategy has resulted in a 2-step total synthesis of (±)-ulodione A and the prediction of two potential natural products, (±)-ulodiones C and D. This work was guided by computational investigations into the selectivity of a proposed biosynthetic Diels-Alder dimerization, which was then utilized in the chemical synthesis. This...

[1001‐58‐7] C3H5NS (MW 87.14) InChI = 1S/C3H5NS/c4‐2‐1‐3‐5/h5H,1,3H2 InChIKey = FCTXEFOUDMXDPD‐UHFFFAOYSA‐N (sulfur transfer reagent) • Alternative Name(s): 3‐mercaptopropanenitrile, 2‐cyanoethanethiol, β‐cyanoethanethiol, 3‐MPN. • Physical Data: bp 87 °C at 15 torr, d 1.06 g mL⁻¹ at 28 °C. • Solubility: soluble in most organic solvents. Partiall...

[42841‐31‐6] C6H8N2S2 (MW 172.26) InChI = 1S/C6H8N2S2/c7‐3‐1‐5‐9‐10‐6‐2‐4‐8/h1‐2,5‐6H2 InChIKey = HHEYGEJOMQFDFN‐UHFFFAOYSA‐N (sulfur transfer reagent) • Alternative Name(s): 3,3′‐disulfanediyldipropanenitrile, S,S′‐di(2‐cyanoethyl)disulfide, di(2‐cyanoethyl)disulfide, 3,3′‐dithiobis(propionitrile), 3,3′‐dithiobispropionitrile, 3,3′‐dithiodipropi...

The C−H functionalisation approach to the synthesis of dibenzofurans is hampered by a number of problems. Herein we describe the evolution of a cheap, bench stable quinoline ligand, which obviates most of the current limitations and allows for a high yielding synthesis of a range of valuable dibenzofurans. Dibenzofurans are important motifs in natu...

A one-pot, tandem Wittig hydrogenation of aldehydes with stabilized ylides is reported, representing a formal C(sp3)-C(sp3) bond construction. The tandem reaction operates under mild conditions, is high yielding, and is broad in scope. Chemoselectivity for olefin reduction is observed, and the methodology is demonstrated in the synthesis of lapatin...

Exploiting the reversibility of chemical processes is a long-standing tactic of organic chemists, and permeates most areas of the discipline. The notion that oxidative addition of Pd(0) to Ar–X bonds can be considered an irreversible process has been challenged, periodically, over the last 30 years. Recent examples of methodologies that harness the...

The quinoline nucleus occurs in many natural and synthetic pharmacologically active compounds, and is ranked 22 nd in the top 100 most frequently used ring systems present in FDA approved drugs. Thus, the quinoline motif is considered a privileged biological scaffold, utilised by synthetic chemists to build molecular complexity, and ultimately impr...

An improved synthesis of the antiviral drug adefovir is presented. Problems associated with current routes to adefovir include capricious yields and a reliance on problematic reagents and solvents, such as magnesium tert-butoxide and DMF, to achieve high conversions to the target. A systematic study within our laboratory led to the identification o...

Chapter One of this thesis presents a consolidated review of methods for the formation of phosphorus-sulfur bonds. This review focuses on the synthesis of phosphorothioates, phosphonothioates, phosphinothioates and phosphonodithioates which are among the most important sulfur-containing organophosphorus compounds and are central to the work describ...

Efficient S-acylation of thiourea using a variety of acid chlorides is reported. Structurally diverse aryl and alkyl substrates are compatible with this methodology. Confirmation that acylation occurs exclusively­ on the sulfur atom of thiourea is provided by single-crystal X-ray crystallographic analysis.

Methods for the preparation of phosphonothioates, phosphonodithioates, phosphorothioates, phosphinothioates and related compounds are reviewed. The application of these compounds as synthetic intermediates is also discussed.

Herein, we report the synthesis of a range of S,S-dialkyl phosphonodithioates. Symmetrically substituted analogues were readily prepared from the corresponding phosphonic dichlorides in good to moderate yields, while unsymmetrically substituted variants were obtained by a sequential alkylation-deprotection-alkylation strategy.

The incorporation of fluorine into a target molecule may have a considerable impact on its reactivity, selectivity, biological activity and physical properties. This is especially true in medicinal chemistry where fluorine is often employed as a bioisostere of hydrogen and where many important drug compounds also feature heteroaromatic rings. This...