Herein, we introduce a new platform for alkene carboxy-alkylation. This reaction is designed around CO2•– addition to alkenes followed by radical polar crossover, which enables alkylation through carbanion attack on carbonyl electrophiles. We discovered that CO2•– adds …
Publication
5/13/2024 – Congratulations to Karina and Minji as well as our collaborators from the Gutierrez group (Achyut and Ángel) on the disclosure of the mechanism for Z-selective allylic functionalization from Thianthrenium salts!
A detailed mechanistic study of the Z-selective allylic functionalization via thianthrenium salts is presented. Kinetic analyses, deuterium labeling experiments, and computational methods are used to rationalize the observed reactivity and selectivity. We find that the reaction …
5/15/2023 – Congratulations to Sara, Jimin, Y, and Camille on developing a new catalytic system that unlocks hydrocarboxylation for unactivated alkenes!
Herein we disclose a strategy to promote the hydrocarboxylation of unactivated alkenes using photochemical activation of formate salts. We illustrate that an alternative initiation mechanism circumvents the limitations of prior approaches and enables hydrocarboxylation of …
4/6/2023 – Congratulations to Dylan, Céline, Casey, and Ilia on developing a new platform for alkene aminofunctionalization!
Modular strategies to rapidly increase molecular complexity have proven immensely synthetically valuable. In principle, transformation of an alkene into a dielectrophile presents an opportunity to deliver two unique nucleophiles across an alkene. Unfortunately, the selectivity …
3/16/2023 – Congratulations to Minji, Diana, Karina, Uriel, Alison, and Ilia on developing a diastereoselective cyclopropanation method using the electrochemical dication pool strategy!
Cyclopropanes are desirable structural motifs with valuable applications in drug discovery and beyond. Established alkene cyclopropanation methods give rise to cyclopropanes with a limited array of substituents, are difficult to scale, or both. Herein, we …
2/25/2023 – Congratulations to Oliver, Alyah, Myriam, Charles, and Desiree on their work to develop a practical deoxygenation protocol with formate and light (and an acid promoter)!
A new protocol for alcohol deoxygenation that functions across a wide range of alcohol structures is reported. This approach combines the reductive potency of carbon dioxide radical anion with acidic additives to promote the kinetically …
12/23/2022 – Congratulations to Myriam and Sara on their work on heteroarene hydrocarboxylation reaction that translates 2D heterocycles into versatile 3D analogs. Out on the rxiv now!
The rapid preparation of complex three-dimensional (3D) heterocyclic scaffolds is a key challenge in modern medicinal chemistry. Small molecule therapeutic candidates with increased 3D complexity, on average, possess a higher probability of clinical success. However, …
11/9/2021 – Congratulations to Diana and Karina on their work coupling alkenes and amines to form (Z)-allylic amines. Out on the rxiv now!
Allylic amines are valuable synthetic targets en route to diverse biologically active amine products. Current allylic C–H amination strategies remain limited with respect to the viable N-substituents. Herein we disclose a new electrochemical process to …
7/22/2021 – Congratulations to Sara on her work splitting formate into H• and CO2•– to hydrocarboxylate alkenes. Out on the rxiv now!
Herein we disclose a new photochemical process to prepare carboxylic acids from formate salts and alkenes. This redox-neutral hydrocarboxylation proceeds in high yields across diverse functionalized alkene substrates with excellent regioselectivity. This operationally simple procedure …
6/22/2021 – Congratulations to Dylan, Diana, and Minji on their work on aziridine synthesis through coupling unactivated alkenes and primary amines via metastable dicationic intermediates. Out in Nature now!
Aziridines, three-membered nitrogen-containing cyclic molecules, are important synthetic targets. Their significant ring strain and resultant proclivity towards ring opening reactions makes them versatile precursors to diverse amine products and, in some cases, the aziridine functional group itself imbues important …