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

June 27 at Conn College New London CT #PfizerChemistry #MerckChemistry @boehringerus #BMSChemistry & @ACS_CVS are hosting the 7th Annual Symposium on Applied Synthesis featuring Ryan Shenvi (Scripps) & Martin Tomanik (NYU) Slots for student talks available #ChemSky https://www.cvs-acs.org/event-details/7th-annual-symposium-on-applied-synthesis

June 27 at Conn College New London CT #PfizerChemistry #MerckChemistry
@boehringerus #BMSChemistry & @ACS_CVS are hosting the 7th Annual Symposium on Applied Synthesis featuring Ryan Shenvi (Scripps) & Martin Tomanik (NYU)
Student talks available
#ChemSky Reg is open: www.cvs-acs.org/event-detail...

Ni-Catalyzed Cyanation of (Hetero)Aryl Electrophiles Using the Nontoxic Cyanating Reagent K4[Fe(CN)6] A Ni-catalyzed cyanation of aryl halides using potassium ferrocyanide (K4[Fe(CN)6]) as a nontoxic cyanide source has been developed. Key features of this method include the use of biphasic aqueous con...

Cool #ACSCatalysis from #BMSChemistry on Ni-catalyzed cyanation with K- ferrocyanide - a low tox CN source. Also the reaction is done in nButyl acetate - the best solvent b/c it smells amazing!

Advancing Base Metal Catalysis: Development and Execution of a Ni-catalyzed Borylation/Pd-catalyzed Suzuki Telescoped Process The development and execution of a nickel-catalyzed borylation/palladium-catalyzed Suzuki telescoped process utilizing the inexpensive NiCl2·6H2O precatalyst for the borylation step are reported. The ...

I see a pattern here...happy to share another story about advancing Base Metal Catalysis on scale! This time, a Ni-Borylation followed by a Pd-Suzuki coupling, Ni and Pd can definitely be friends 😊 Congrats to all the co-authors! #BMSChemistry pubs.acs.org/doi/10.1021/...

Read it yesterday! Great paper and yes KOPiv is awesome in borylations and trapping with diethanolamine was a godsend in a recent project
Nice work by Jake and #BMSChemistry

Development of an Inherently Safe and Scalable Nickel-Catalyzed Borylation Process of an Aryl Sulfamate A safe and scalable synthesis of A, a key aryl boronate ester intermediate toward an immunology asset udifitimod, via a Ni-catalyzed Miyaura borylation is reported. High-throughput experimentation, design of experiment, and reagent stability/compatibility studies were used to optimize the reaction conditions and furnish the borylation of aryl sulfamate B in 80–85% yield and >98% purity/potency. Significant hydrogen off-gassing was observed during the reaction, metal remediation, and crystallization steps of the first-generation process, and efforts were made to quantify, understand, and mitigate this off-gassing to ensure a safe and reliable scale-up. Two multikilogram batches of the process were successfully run to afford A in an average 85% yield, >99% potency, and ≤28 ppm residual Ni. Using the mechanistic learnings from this work, a second-generation process was developed which significantly reduced hydrogen off-gassing at all steps of the process, as well as increasing final yield and reducing process mass intensity. This second-generation process was demonstrated on a 1 kg scale to afford the product in 90% yield, >99% purity/potency, and 50 ppm residual Ni.

So excited to share our work on learning more about EAM catalysis on scale! Featuring two of our favorites: nickel and boron 🤓 Who knew there were so many ways to make hydrogen in a borylation reaction 🤪 Congrats to all the co-authors! #BMSChemistry pubs.acs.org/doi/10.1021/...