Understanding Catalyst Activation Drives Transition from Iridium to Manganese Catalyzed Hydrogen Autotransfer Chemistry As an alternative to iridium catalysts, a procedure to access and employ a more earth-adundant Mn2(CO)10-derived pincer complex was successfully demonstrated in the synthesis of a complex pharmaceutically relevant ketone from milligram to 500g scales. Mechanistic studies revealed that the dissociation of CO driven by light is a critical step in forming the active catalyst. This robust and mechanistically informed method reliably promotes hydrogen autotransfer of alcohols, catalyzing a diverse array of C–C and C–N bond formations. This emphasizes the importance of precatalyst selection and understanding catalyst activation to enable rapid and successful uptake of novel methods in sustainable catalysis.

Really nice work here in #OrgLettASAP from #BMSChemistry enabling 1st row Manganese instead of Iridium in hydrogen borrowing. Lots of good mechanism and optimization in here #ChemSky

Hacking 3D printers as laboratory robots The emergence of affordable and reliable 3D printers has enabled laboratories to optimize setups, print custom parts, accelerate research, and rapidly prototype. A new movement has emerged in the past...

How to make your own robot!
A review of people making awesome lab robots out of commercial 3D printers. Thank you @vsaggiomo.bsky.social and Sander for inviting me to help write this paper in @digital-discovery.rsc.org.

Beep boop! 🤖 #chemsky
doi.org/10.1039/D5DD...

Room-Temperature Decarboxylative Amination of Electron-Deficient (Hetero)Aromatic Carboxylic Acids Decarboxylative amination reactions offer the opportunity to access (hetero)aromatic amines from readily available carboxylic acid starting materials. However, the reliance of the Curtius rearrangemen...

Curtius without azide!
Very cool transformation from the Hoover Lab @ Minnesota out in #OrgLettASAP with @jesstheligand.bsky.social showings e-poor (Her)Ar-CO2H can undergo a Curtius-type rearrangement to her-Ar amines with NFSI as oxidant at RT!
Wonderful scope - well done all
#ChemSky

Let me know if you find a fix...so far, I haven't!

Inspired by the way nature modifies tyrosine residues, we've developed a simple method using a hypervalent iodine reagent to perform an umpolung of the phenolic core, generating ortho-quinone intermediates that can be readily trapped to accomplish either skeletal or peripheral modifications!

Our first venture into short peptide diversification is now online 😁 doi.org/10.26434/che...

Does anyone else have issues with ChemRxiv's RSS feed after their website's update? I didn't get any content update since last week. I'm using The Old Reader as RSS reader.
#chemchat #chemsky

Collective asymmetric synthesis of the Strychnos alkaloids via thiophene S,S-dioxide cycloadditions - Nature Chemistry Thiophene S,S-dioxides are excellent substrates for cycloaddition reactions, but underused in target-oriented synthesis. Here the authors show how these heterocycles enable the asymmetric synthesis of...

Amazingly efficient synthesis of the strychnine family of alkaloids from Ed Anderson Group at @oxfordchemistry.bsky.social
These thiophene-dioxides are really useful synthons
#ChemSky #ChemChat
@natchem.nature.com

Process Development and Scale-Up of RLY-2139: A Selective CDK2 Inhibitor Targeting ER+/HER2– Breast Cancer RLY-2139 is a potent and selective orthosteric CDK2/Cyclin E inhibitor in development for the treatment of ER+/HER2– breast cancer. It showed an on target IC50 of 4 nM for CDK2/CycE and good biochemic...

BCP IN OPRD!!
It’s finally happened- kg scale up of a BCP
(Ok it’s prob happened already but this is the first one I’ve seen)
Also,the OPRD paper for the green THF fragment came out recently and is excellent work (link in reply)
#ChemSky #ChemChat

We had a great start of the year 😁 The final version of this work is now published. Congrats once again Michael, Atha, and Cedric!
pubs.acs.org/doi/10.1021/...

Fixing A Reaction

some seriously artisanal Derek this morning #chemchat www.science.org/content/blog...

#chemsky #chemchat

And here it is – Annulative Editing – aka The Monster Mash. What a super collab #PfizerChemistry & @sarponggroup.bsky.social
In 1 pot, activated pyrimidines with bis-nucleophiles like amino-pyrazoles & other small hets to deliver 6/5 hets and other useful products
#MyFirstJACS
#ChemSky #ChemChat

Oxygen migration into carbon–carbon single bonds by photochemical oxidation - Nature Synthesis Heteroatom insertions into chemically inert carbon–carbon single bonds are rare compared to their unsaturated analogues. Now, ligand-to-metal charge transfer offers a promising entry point for oxygen ...

Really excited to see this in print - super work here by the wonderful team here from the @uwyoongroup.bsky.social
It was a real pleasure to watch this work evolve from a "what if" discussion to a @natsynth.nature.com paper
I truly appreciate being included #Chemsky

Deep-Red to Near-Infrared Light-Driven Radical Generation from Organoboron Compounds via Ligand-Induced Direct Excitation Catalysis We report a catalytic strategy for generating carbon-centered radicals from organoboron compounds under deep-red to near-infrared (DR to NIR) light irradiation via direct excitation of substrate–catal...

Our new paper is out in #JACS (@jacs.acspublications.org)! Deep-red to NIR light enables carbon radical generation via ligand-induced direct excitation catalysis. Congrats Yusuke, Kanji, and the team! pubs.acs.org/doi/10.1021/...

New @chemrxiv.org, a collaboration with @honggen-wang.bsky.social and group alum, now asst prof. Myojeong Kim: the first true catalytic interception of isodiazene-generated primary-amine-derived radicals. The key is an N-F reagent that enables productive chain carrying!

doi.org/10.26434/che...

www.organic-chemistry.org/abstracts/li...
A transition-metal-free ring expansion of gem-difluorinated cyclopropyl N-tosylhydrazons provides gem-difluorinated cyclobutenes.

🚨New paper🚨We have developed a simple method for the oxidative cleavage of beta-substituted primary alcohols in flow by using a solid-supported hypervalent iodine catalyst and a mild oxidant. Congrats Michael, Atha, and Cedric!
chemrxiv.org/engage/chemr...

Safety Letter: Evaluation of the Popular Oxidant 2-Iodoxybenzoic Acid (IBX) 2-Iodoxybenzoic acid (IBX) is a versatile oxidant used in chemical synthesis. It has been employed as a reagent in more than 1400 publications since its initial use as an oxidant described in 1994. Wh...

Excellent safety letter in #OrgLettAsap today from the Garg Lab (UCLA) and #MerckChemistry on the hazards of IBX - please read
And thank you to Org Lett for publishing this informative article
#ChemSky

I’m proud to share that my group has received a Starting Grant from @erc.europa.eu, which will enable us to explore new organophotomediated reactions, and deeply grateful to my group and the many colleagues who helped with the application.

Congrats to @fruepp.bsky.social, Vasily Grebennikov, Mykola Avramenko, Marc-Olivier Ebert "Kinetic, Spectroscopic, and Computational Investigation of Oxidative Aminative Alkene Cleavage Reveals an N-Iodonium-Iminoiodinane Pathway" now @chemrxiv.org - chemrxiv.org/engage/chemr...

Congrats to Ann-Sophie Paschke, @ybraegger.bsky.social, Bence Botlik, Erich Staudinger, @origreen.bsky.social! "Carbon-to-nitrogen atom swap enables direct access to benzimidazoles from drug-like indoles". www.nature.com/articles/s41.... @natchem.nature.com.

As asymmetric sulfur(VI) derivatives become more prevalent in the chemical sciences, especially in aza-derivatives, sulfoximines, sulfonimidamides, we have reviewed "The stereochemistry of substitution at S(VI)"
doi.org/10.1039/D5QO...
with Ollie Symes, @orgchemfront.rsc.org

Do Amino-Oxetanes Resemble Amides?
Check out our Matched Molecular Pairs study in
@chemrxiv.org comparing properties and structure.
Congrats @hikaruishikura.bsky.social and coworkers, in collaboration with Pfizer.
doi.org/10.26434/che...

Many Thanks for the wonderful highlight!!

Reimagining Advanced Chemistry Education: A Community-based Approach to Course Design for Modern Learners Chemistry education at the graduate level and beyond faces the formidable challenge of a boundless and constantly expanding frontier of knowledge on many fronts. While modern learners have an increasi...

Today after years of work and a tight collaboration between >40 chemists in academia and industry, we are thrilled to share the story of how our Advanced Organic Chemistry course and other courses were created in the Journal of Chemical Education!

Link: doi.org/10.1021/acs....

📢pls share
We are hiring! New opening for a W2 Professor in "experimental inorganic chemistry" @unibonn.bsky.social
Deadline Oct. 10 t.co/EqMLA0fCuC

Automated Determination of the Molecular Substructure from Nuclear Magnetic Resonance Spectra Using Neural Networks Nuclear magnetic resonance (NMR) spectroscopy is an indispensable tool for determining the structural characteristics of a molecule by analyzing its chemical shifts. A wealth of NMR spectra therefore exists and continues to amass on a daily basis, at an ever-increasing rate owing to the progressive automation of chemical analysis. This growth and automation have led to the data analysis step in NMR spectroscopy becoming the main bottleneck in the structural characterization of a new chemical compound. In particular, the data interpretation step is slow and prone to error as it requires manual examination by a suitably trained scientist. Machine learning (ML) methods could overcome this bottleneck, pending that they can automatically correlate the collection of peaks in an NMR spectrum with the substructure of its subject molecule. This study explores the art of the possible using three types of ML methods that are based on neural-network architectures: a multilayer perceptron (MLP) + long short-term memory (LSTM) neural network, a convolutional neural network (CNN), and an MLP + recurrent neural network (RNN). NMR spectrum–structure correlations were encoded into each type of neural network using two forms of molecular representation, one employing functional groups and the other using a novel neighbor-based method. These models were trained on 34,503 and 17,311 experimental 13C and 1H NMR spectra, respectively. The influence of incorporating metadata about experimental conditions (NMR field strength, temperature, and solvent) into the neural-network model was also investigated. The models incorporated coupling constants as a proxy for spectral intensities in the case of 13C NMR spectra. We found that the MLP + LSTM model achieved the highest accuracy (88%) when trained on 13C NMR spectra and incorporating experimental metadata (compared to 77% without incorporating it). While the CNN model performance was slightly lower (86% accuracy), it determined molecular substructures in one-third of the computational run time compared to the MLP + LSTM model. Thus, the CNN model emerged as the practically best model when considering performance, time, and cost.

Liu & Cole use neural networks on 50k+ ¹³C/¹H NMR spectra with metadata to predict molecular substructures. Their MLP+LSTM model hit 88% accuracy; CNNs reached 86% in one-third the time, enabling fast, automated NMR analysis for chemistry and drug discovery. pubs.acs.org/doi/full/10....

Sulfur fluoride exchange with carbon pronucleophiles Aryl alkyl sulfones are an important class of compounds in drug discovery; thus, new methods toward their synthesis are desirable. A general sulfur fluoride exchange (SuFEx) method to couple aryl sulf...

SuFEx welcomes new coupling partners - carbon pronucleophiles now in @chemicalscience.rsc.org . Congrats to Ball Lab students Joe Novicku and Matt Teeter and Pfizer colleagues Alistair, Tom, Neil, ans @chrisamende.bsky.social on the great work! #MyFirstChemSci

pubs.rsc.org/en/content/a...