Palladium‐Catalyzed α‐Arylation Reactions in Total Synthesis

Abstract

The development of palladium‐catalyzed α‐arylation of carbonyl compounds has emerged as a new avenue in the design of new routes for the synthesis of natural products and active pharmaceutical ingredients (APIs). In many cases, syntheses based on α‐arylation strategies provide elegant routes in terms of increasing the overall yields, improving the synthesis scope, and decreasing the number of steps. This microreview aims to highlight the importance of palladium‐catalyzed α‐arylation methodologies, covering a range of notable reported examples of the total syntheses of structurally important compounds, thereby highlighting the importance of this powerful methodology for key steps in organic synthesis.

Recyclable supported Pd-NHC catalytic systems for the copper-free Sonogashira cross-coupling in flow

“…NMR spectra were obtained at the Servei de Recursos Científics i Tècnics (SRCT), URV, with Varian (Agilent) Mercury VX400 or NMR System400 400 MHz spectrometers and calibrated to residual solvent peaks. Chemical and shifts for 1 H and 13 C{ 1 H} NMR spectra are reported relative to TMS. ICP analyses were conducted at the SCRT using an ICP-OES Spectro Arcos instrument.…”

“…[1][2][3][4][5][6] These coupling processes had a transformative impact on chemicals industries and have been employed in a number of industrial applications [7,8] as well as reported in numerous publications on the syntheses of complex organic molecules and materials, such as natural products, fine chemicals, drugs, agrochemicals and polymers. [9][10][11][12][13] In most cases, the new reaction development was performed under conventional batch synthesis conditions, whereas most chemical companies, especially in the pharmaceutical and speciality chemicals fields, are rapidly developing capability in continuous flow manufacturing. [14,15] The use of Pd-based catalysts under flow conditions represents specific challenges of production of solids and leaching of Pd into the products, which complicate the development of generic, efficient manufacturing protocols.…”

Humanity in Science Award: P. H. Seeberger und A. Seidel‐Morgenstern / Henry J. Albert Award: T. J. Colacot / L'Oréal–UNESCO For Women in Science Awards: Y. Xie und C. V. Robinson

“…Colacot, der in dieser Rubrik vorgestellt wurde, als ihm der Applied Catalysis Award der RSC verliehen worden war,3a hat außerdem den Award in Industrial Chemistry der ACS für 2015 erhalten und wird 2016 Empfänger der Medaille der indischen chemischen Forschungsgemeinschaft (CRSI) sein. Er hat kürzlich im European Journal of Organic Chemistry einen Microreview über palladiumkatalysierte α‐Arylierungen veröffentlicht 3b …”

Accessing the Ene–Imine Motif in 1H-Isoindole, Thienopyrrole, and Thienopyridine Building Blocks

“…Molecular building blocks possessing discrete conjugated segments that can be combined with other conjugated molecular units in a facile manner are widely utilized in pharmaceuticals 1 and organic electronics. 2 Moieties such as diketopyrrolopyrrole 1 and isoindigo 2 are widely used in the latter field for the synthesis of conjugated small molecules and polymers.…”