In this paper, just reported in Organometallics, we describe the results of a computational investigation that shed light on the catalyst structure–activity and selectivity relationships for our recently developed Rh(I)-xantphos-catalyzed transfer C–H borylation of alkenes (c.f., Chem Catal. 2022, 2, 762-778). The study provides guidelines for the rational development of new catalysts to further enhance the performance of the catalytic system and address the remaining challenges.
After an excellent presentation and a thorough scientific discussion with the jury members – Prof. Bill Morandi, Prof. Bas de Bruin, Prof. Philippe Dauban, Dr. Joanna Wencel-Delord, and Prof. Thomas Ebbesen, Sebastián successfully defended his PhD thesis and was granted a doctorate title. Congratulations and good luck for the future! Special thanks to the jury members!
Our recent publication on “Transfer C–H borylation of alkenes under Rh(I) catalysis: Insight into the synthetic capacity, mechanism, and selectivity control.” is featured on the cover of the April issue of Chem Catalysis!
In this paper, we present a broadly applicable method for the C–H borylation of various alkenes, that is, a valuable transformation in the synthesis of fine chemicals, such as pharmaceuticals and agrochemicals. Importantly, the reaction tolerates a plethora of functional groups and can be used for the late-stage functionalization of complex bioactive molecules, such as derivatives of zearalenol and brompheniramine. The study provides insight into the reaction mechanism and the features controlling the selectivity, thereby setting the stage for the development of other related valuable reactions.
In this communication, we report our recent study on the isoselective hydroformylation of propylene – an industrially desired but elusive transformation – enabled by non-canonical iodide-assisted palladium catalysis. The publication was selected by the editors as a Hot Paper.
In this review article in a special issue of Synthesis – “Bürgenstock Special Section 2021 – Future Stars in Organic Chemistry’, we provide an overview of different approaches in the field of C–H borylation reactions mediated by group 9 metal-based catalysts that target the control of the activity and the selectivity of the reaction, with the main focus on recent studies.
In this Perspective, we discuss the challenges of controlling the stereoselectivity of reactions occurring through free-radical intermediates. In the context of the recent work of Yang et al. (Science374, 1612 (2021)), we highlight the opportunities of conducting such reactions (and beyond!) in the presence of engineered enzymes,
In the invited mini-review in EurJOC, Yang and Michel analyzed the field of Pd-catalyzed hydroformylation!
Hydroformylation of alkenes and alkynes with syngas represents a method of choice to furnish valuable aldehydes with 100% atom-economy from readily available building blocks. Although the field is dominated by Rh- and Co-catalysis; complexes of many other metals were also shown to be catalytically competent. Here we review the studies of hydroformylation under Pd-catalysis, starting from the seminal reports up to the most recent examples. Special emphasis is paid to the unique regio- and chemoselectivities of Pd-based methods, which are difficult to achieve with the conventional hydroformylation protocols. Different mechanistic proposals are presented along with a summary of their experimental andc omputational support. Finally, the user-friendly methods using surrogates of syngas are discussed as well. Overall, the mini-review aims to present unique opportunities and remaining challenges of Pd-catalyzed hydroformylation reactions for their prospective applications in fine-chemical synthesis.
In this Letter, we report the enantioselective synthesis of secondary benzylic alcohols and diarylmethanols by α-arylation of primary aliphatic and benzylic alcohols under sequential catalysis. The strategy integrates a Ru-catalyzed hydrogen transfer oxidation and a Ru-catalyzed nucleophilic addition in a one-pot fashion. The method can be applied to various alcohols and aryl nucleophiles tolerating a range of functional groups, including secondary alcohols, ketones, alkenes, esters, NH amides, tertiary amines, aryl halides, and heterocycles. Overall, the study shows the potential of multicatalysis to enable transformations that are challenging for classic catalysis.