The Hartwig Group

Our postdoc Willi Amberg built SynStrategy, a learning tool that categorizes 500+ reactions by functional group with 400+ total synthesis examples. If you’re into #OrgChem, check it out (it’s free)!

iOS:  apps.apple.com/de/app/synst...
Android: play.google.com/store/apps/d...

#ChemSky

Check out this post by @dereklowe.bsky.social where he uses our new method from our recent @jacs.acspublications.org paper! Thanks for trying it out!

Unleashing the Power of Potassium 2-Ethylhexanoate as a Mild and Soluble Base for Pd-Catalyzed C–N Cross-Coupling The formation of C–N bonds by Pd-catalyzed cross-coupling is one of the most widely practiced reactions in chemical synthesis. Typical reaction conditions involve either a strong base, which limits the scope of substrates, or an insoluble, inorganic base, which complicates running reactions on a large scale. Reaction conditions for C–N couplings with a base that is both mild and soluble are needed. We report the discovery of a combination of a phosphorinane ligand (L147) and a soluble carboxylate base, potassium 2-ethylhexanoate (K-2-EH), which leads to the coupling of a wide range of base-sensitive coupling partners. To explore the enhanced substrate scope of the reaction with this base and catalyst, we evaluated the scope using representative reactants selected from published partners, using chemical descriptors and clustering to ensure their chemical diversity. These results show that the combination of this phosphorinane ligand and K-2-EH can couple primary aliphatic amines, amides, sulfonamides, and heteroaromatic nucleophiles as well as acidic secondary nitrogen nucleophiles, such as arylamines, heteroarylamines, and amides, with a range of electrophiles. A side-by-side comparison to form selected coupling products in the presence of a range of previously reported bases and ligands showed that the products that decomposed under standard reaction conditions were stable with K-2-EH as a base. Finally, models of quantitative structure–reactivity relationships, trained on ligand screening data, were developed to help reveal the structural features that engender reactivity.

Excited to share our new method for Pd-catalyzed C–N cross-coupling, now published in @jacs.acspublications.org!

This method utilizes an inexpensive, mild, and soluble base suitable for small & large scales with excellent functional group tolerance across chemical space.

doi.org/10.1021/jacs...

Unleashing the Power of Potassium 2-Ethylhexanoate as a Mild and Soluble Base for Pd-Catalyzed C–N Cross-Coupling The formation of C–N bonds by Pd-catalyzed cross-coupling is one of the most widely practiced reactions in chemical synthesis. Typical reaction conditions involve either a strong base, which limits the scope of substrates, or an insoluble, inorganic base, which complicates running reactions on a large scale. Reaction conditions for C–N couplings with a base that is both mild and soluble are needed. We report the discovery of a combination of a phosphorinane ligand (L147) and a soluble carboxylate base, potassium 2-ethylhexanoate (K-2-EH), which leads to the coupling of a wide range of base-sensitive coupling partners. To explore the enhanced substrate scope of the reaction with this base and catalyst, we evaluated the scope using representative reactants selected from published partners, using chemical descriptors and clustering to ensure their chemical diversity. These results show that the combination of this phosphorinane ligand and K-2-EH can couple primary aliphatic amines, amides, sulfonamides, and heteroaromatic nucleophiles as well as acidic secondary nitrogen nucleophiles, such as arylamines, heteroarylamines, and amides, with a range of electrophiles. A side-by-side comparison to form selected coupling products in the presence of a range of previously reported bases and ligands showed that the products that decomposed under standard reaction conditions were stable with K-2-EH as a base. Finally, models of quantitative structure–reactivity relationships, trained on ligand screening data, were developed to help reveal the structural features that engender reactivity.

Cool work here in #JACSasap from the @hartwiggroup.bsky.social and AbbVie improving C-N couplings with a lipophilic/soluble alkyl carboxylate as the base
Will be helpful for parallel applications where liquid dosing is important as well as for flow synth
#ChemSky #ChemChat

Electronic Activation Enables the Borylation of Alkyl C–H Bonds in Saturated Nitrogen Heterocycles ( @hartwiggroup.bsky.social ): pubs.acs.org/doi/10.1021/... ( @jacs.acspublications.org ).

Site-, Stereo-, and Chemoselective Enzymatic Halogenation of Terpenoids by a Substrate Masquerade Enzymatic halogenation of C–H bonds is a promising approach to synthesize chlorine-containing compounds. However, few halogenases chlorinate C(sp3)–H bonds of molecules lacking a carrier protein, and ...

This is such a neat idea from the @narayanlab.bsky.social and the @hartwiggroup.bsky.social now in #JACSasap fooling enzymes with a removable binding ligand to accept non-native substrates #ChemSky

Oski's B-day Bear-a-thon 2025 Let's help students flourish and belong at Cal!

Support UC Berkeley’s College of Chemistry! givingday.berkeley.edu/giving-day/1...

Catalytic Borylation of Poly(vinyl chloride) Produces Adhesive Materials ( @hartwiggroup.bsky.social ): pubs.acs.org/doi/10.1021/... ( @jacs.acspublications.org ).

You can always expect something cool from @hartwiggroup.bsky.social and this one is no exception. Cu-catalyzed borylation of waste PVC creates strong adhesives for glass and metal - 5x more than commercial glue! #Chemsky

Register early and save

Excited to hear from our keynotes: Cyrille Boyer, @hartwiggroup.bsky.social @dr-imari-bsky.social Karen Wooley @tamu.bsky.social @CellSymposia #CSPlastics2025
Register before August 1 and take advantage of our early bird rates: http://dlvr.it/TLvZvS

Congratulations to our amazing new doctors this year! Jeremy Nicolai, RJ Conk, Isaac Joyner, John Brunn, Christina Pierson, and Nico Ciccia! 🎓🎉🎓

Join us to see John discuss some of our current work combining #MachineLearning with transition metal catalysis!

John Hartwig, chemist: ‘The situation for science in the United States is terrible, these are the steps of authoritarian regimes to take power’ The scientist talks to EL PAÍS about the key advances in the production of new pharmaceuticals

english.elpais.com/science-tech...

The situation for science in the U.S. is terrible. How should I put this because I don’t want to make everybody flee our country, but I do think it needs to be clear to the public. They’re not funding grants from the National Institutes of Health, including in backdoor ways, like blocking committees from meeting that make decisions about the grants. I have three post-doctoral students who have fellowship applications that are not even being reviewed. I also have a $3.5 million grant that was recommended for funding, for plastics recycling. There’s been a “communications pause.” I don’t know if it’ll still go forward, or maybe it never gets funded. [If that happens] we wouldn’t have the opportunity to try to pursue the commercial viability of this chemical recycling that we developed and that others would be able to contribute to.

Those discoveries can be made in a university, or they can be made in industry, but the people in industry who made those discoveries went to universities and got advanced degrees in the sciences and then went off and started the new biotech company that discovers a drug that gets developed into affecting human health. That is how the whole economy works. Companies such as Google and many others in the technology sector rely on people trained in these institutions. If we pull the plug on training, where’s the United States’ position as a technology leader? There’s this feeling: these are the kinds of steps of authoritarian regimes to take power. And we’re just watching it happen. How do we stop this?

This whole interview is outstanding

chemsky 🧪

english.elpais.com/science-tech...

Unleashing the Power of Potassium 2-Ethylhexanoate as a Mild and Soluble Base for Pd-catalyzed C-N Cross-Coupling

Authors: William Lambert, Stephanie Felten, Nicholas Hadler, N. Ian Rinehart, Rafal Swiatowiec, Gregory Storer, Jeremy Henle, Mark Servos, ...
DOI: 10.26434/chemrxiv-2025-59c10

If you want to know more about the Hartwig group chemistry, the Organic Chemistry Days (JCO 2025) in October are the place to be! jco2025.com/speakers/

Registration will open very soon.

Palaiseau - Ecole Polytechnique (France)
29 - 31 October 2025

@hartwiggroup.bsky.social
@scf-dco.bsky.social

Send a cover letter, CV, and research summary to jhartwig@berkeley.edu & jisu@lbl.gov (subject: “Postdoc Opening on Polymer Deconstruction”). Seeking candidates of all backgrounds with a strong record of success, independence & creativity.

We are seeking candidates with backgrounds and interests on the more chemical side or the more engineering side of chemical engineering (or both) to develop multiple aspects of this research topic. The research is a collaboration between UC Berkeley and LBNL.

Polyolefin waste to light olefins with ethylene and base-metal heterogeneous catalysts The selective conversion of polyethylene (PE), polypropylene (PP), and mixtures of these two polymers to form products with high volume demand is urgently needed because current methods suffer from lo...

Our research group, together with Alex Bell, Ji Su, Corine Scown, will be recruiting postdoc candidates to conduct research on aspects of the polymer deconstruction process that we recently published in Science (www.science.org/doi/10.1126/...).

Outstanding team: Jeremy Demarteau, Alex Epstein, Laura Reed, Nico Ciccia, John Hartwig, and Kristin Persson @hartwiggroup.bsky.social

Circularity in polydiketoenamine thermoplastics via control over reactive chain conformation Controlling polymer chain conformation dictates reactivity and recyclability.

Just out in Science Advances @science.org! Chemical recycling of plastics to monomer accelerated through oxy-functionalization remote from the bond undergoing cleavage. Polymer conformation plays dominant role. @molecularfoundry.bsky.social @berkeleylab.lbl.gov www.science.org/doi/10.1126/...

Read the full press release and learn more here. #ARPAEVISION

arpa-e.energy.gov/news-and-eve...

Our project aims to translate our recently developed process for the chemical recycling of polyolefins to industrial scales. This process converts polyolefins (the most common polymers in waste plastics) to important chemical feedstocks, including those used to make new polymers.

We’re thrilled to share that our team at the University of California, Berkeley was selected through @ARPAE's Vision OPEN 2024 program, which creates groundbreaking solutions across the energy spectrum.