Electrifying chemistry...

La Jolla, CA
Radical cross-coupling, simplified. No specialized equipment. No exogenous redox. No stoichiometric organometallics. The best part is no part.  A perspective on the field, appearing today in @ChemRxiv : chemrxiv.org/doi/full/10.264…
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From dynamic tautomers to stable isosteres. Our electrochemical method converts readily available CF₃ alkenes into independently accessible fluorinated isosteres corresponding to keto and enol forms. Now out in JACS! doi.org/10.1021/jacs.6c15284
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Ni-Catalyzed C–H Alkylation of (hetero)arenes: Super simple, broad scope, enabled by sulfonylhydrazides! Appearing today in @ChemRxiv (chemrxiv.org/engage/chemrxiv…). An awesome joint venture with the amazing @EngleLab. Quick Summary: A new method for facile C–H alkylation of a range of (hetero)arenes is described using Ni-catalysis. This reaction takes place at 50 °C, is scalable, tolerates heterocyclic substrates, and can be applied to both primary and complex secondary alkyl donors. Success hinges on the use of sulfonylhydrazide-based alkyl donors that mildly generate alkyl radicals thereby obviating the need for alkyl halide precursors that require more harsh conditions to activate. The demonstrated substrate scope is broad (>70 examples), and the reaction was also applied to natural product synthesis. Mechanistic studies (both computational and experimental) suggest that an asynchronous, amine-assisted C–H activation pathway is operative which may have larger implications for the field.
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Skip the Mitsunobu, go straight to the hydrazide. Our growing collection of sulfonyl hydrazides are the cheapest on the market and get to your bench quickly with same-day shipping. #knightchem #medchem #sulfonylhydrazides
Behind every hydrazide there's a story, and that story is the Mitsunobu reaction.
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The final version of our work is now online in JACS! Scalable total synthesis of nonthmicin and ecteinamycin revealed a dual antibacterial and antitoxin profile against Clostridioides difficile. Many thanks to all our collaborators! pubs.acs.org/jacsat/article/…
Our latest work shows how modern total synthesis can enable therapeutically meaningful discovery, uncovering selective anti-C. difficile activity and toxin-protective effects of structurally complex polyether ionophores. Now available on ChemRxiv: chemrxiv.org/doi/full/10.264…
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Scripps Research, @UCLA and @SuntheticsML have received a $19.5M @NSF award to establish a nationally accessible, fully automated chemistry lab. The AI-enabled “Chemistry Node” will serve as a discovery engine and training tool for a new generation of chemists. More: ow.ly/Zcne50ZFQxA
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Here comes a short review on the current state of electrochemical hydrogenation of arenes and heteroarenes, with a particular focus on how electrochemistry can precisely control partial vs. full reduction of the targeted aromatic rings. Open access link: sciencedirect.com/science/ar…
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Our latest paper is now out in @J_A_C_S! Carbenoid species have had a profound impact on synthetic chemistry and are now indispensable tools for building molecular complexity. Yet one of their smallest main-group relatives, the borylene, has remained notably absent from the synthetic chemist’s toolbox, despite its fascinating and highly unusual electronic structure. Since starting our group, one of our major goals has been to address this challenge and explore the synthetic potential of borylenes. In our work, we report an exceptionally mild and modular approach to borylene generation from simple, readily diversifiable precursors. We then use this platform to explore the cycloaddition chemistry of borylenes with alkenes, providing access to unique fused borirane architectures. This reactivity developed into a chemo- and regioselective strategy for alkene functionalization, with the resulting boriranes serving as versatile synthetic intermediates. We further demonstrate its utility through application to the formal synthesis of natural products. We believe this work takes borylenes one step closer to becoming practical species for synthetic chemistry, and opens the door to many new transformations yet to be discovered. pubs.acs.org/jacsat/article/…
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Two directions. One radical move. Simultaneous two-directional catalytic radical cross-coupling, a great collaboration with Abbvie (@KaidHarper), is out now in @ChemRxiv (chemrxiv.org/doi/full/10.264…) Diacid-derived bis-RAEs undergo Ag–Ni electrocatalytic decarboxylative arylation → functionalized dibenzyl amines & linkers. Diamine-derived bis-sulfonyl hydrazides deliver redox-neutral deaminative RCC → decorated carbon skeletons. Chemoselective. Scalable. Modular access to valuable products from simple, symmetrical starting materials — including PROTAC-style linkers with C–C bonds instead of amides. The classic two-directional logic of @SchreiberStuart, now fully radical.
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Baran Lab retweeted
"Doubly Decarboxylative Asp-Asp Stapling” appearing today in @ChemRxiv : chemrxiv.org/doi/full/10.264… Collaboration with @nagata_yuuya
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When I was in grad school, radicals were synonymous with “messy and uncontrollable”. Modern radical-cross coupling tells almost the opposite story. And the field is still evolving into a new phase. A great review of how far it has come!
Radical cross-coupling, simplified. No specialized equipment. No exogenous redox. No stoichiometric organometallics. The best part is no part.  A perspective on the field, appearing today in @ChemRxiv : chemrxiv.org/doi/full/10.264…
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Really excited to see this Perspective out today! 🚀 Radical cross-coupling carried a hidden tax: redox. Sulfonyl hydrazides changed that paradigm by bringing their own electrons 🎉 Two years later: what comes next and can radical cross-coupling become as intuitive as a Suzuki?
Radical cross-coupling, simplified. No specialized equipment. No exogenous redox. No stoichiometric organometallics. The best part is no part.  A perspective on the field, appearing today in @ChemRxiv : chemrxiv.org/doi/full/10.264…
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Baran Lab retweeted
One C–C bond became our Battle of Thermopylae. Pass closed. 6 mo in, @BaranLabReads hydrazide RCC arrived. Right reaction, right lab, very right timing. 😅 Desymmetrization + ring contraction → (+)-roussoellatide, 11 steps. SI = casualty report 👀 🔗 chemrxiv.org/doi/abs/10.2643…
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RCC to the RESCUE: A rapid, convergent synthesis of roussoellatide enabled by redox-neutral radical cross-coupling, completed by @Nima_Nasiri_. A case study in how RCC prevails when classical polar methods fail. Out now in @ChemRxiv : chemrxiv.org/doi/abs/10.2643…
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More sweet hydrazides: Copper-Mediated Radical Transformation of Protection-Free Glycosylsulfonohydrazide for Access to Diverse Glycosides | Journal of the American Chemical Society pubs.acs.org/doi/10.1021/jac… Stereoselective C1-Arylation of Native Sugars via Ligand-Promoted Nickel Catalysis | Journal of the American Chemical Society pubs.acs.org/doi/10.1021/jac…
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Baran Lab retweeted
We report an Et₃N-enabled electrochemical platform for deep PFAS defluorination and scalable fluoride recovery. Turning forever chemicals into fluorine resources. Now out in JACS! pubs.acs.org/jacsat/article/…
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#TotalSynthesis of Scholarisines A, I, T, and W by Rui Guo, Fan Li, Lin Wang, Mengyu Ba, Zhicong Guo, Weiwei He, and Ang Li at Shanghai Institute of Organic Chemistry in @J_A_C_S pubs.acs.org/jacsat/article/…
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Baran Lab retweeted
Textbook tells you that Cys-conjugation is driven by thiolate. The logic was simple: e-poor acceptor, high pH, more S-, and fast reaction. But our (@BaranLabReads ) reagent reacts fastest under mild acidic pH and was boosted by EDG—the exact opposite!!! Check this out!! 👇
A Kinetics-first Approach Reveals Optimum Vinylaminopyrimidines for Cysteine-Based Antibody Conjugation – an exciting collaboration with @scrippsresearch colleagues @Dawson_Group and the Blackmond group along with BMS – appearing now in @ChemRxiv : chemrxiv.org/doi/abs/10.2643…
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