Together with Prof. Paul Chirik at Princeton and Drs. Eric Simmons and Steve Wisniewski from Bristol Myers Squibb, Keary authored a Perspective in Org. Process Res. Dev. on the importance of academia–industry collaboration in advancing the state of the art in base metal catalysis. The article outlines the various factors that motivate research in base metal catalysis within the pharmaceutical industry and discusses how these challenges can spur innovations reaction, catalyst, and ligand development, such as in the case of our collaborative work on bench-stable Ni(0) pre-catalysts.

For a link to the article, click here: https://pubs.acs.org/doi/10.1021/acs.oprd.3c00025

Today we are pleased to announce publication of a collaborative study with Prof. Yu Lan’s group at Zhengzhou University elucidating the mechanism of nickel-catalyzed conjunctive cross-coupling reactions of alkenes, aryl iodides, and organozinc reagents, which reveals a previously under-appreciated role of the organozinc reagent as a Z-type ligand that facilitates reductive elimination. This revised mechanistic model explains how this type of conjunctive cross-coupling can proceed under such mild conditions without specialized ligand, despite involving a typically challenging C(sp³)–C(sp³) reductive elimination event. Congrats to the entire project team!

For a link to the paper in J. Am. Chem. Soc., click here: https://pubs.acs.org/doi/full/10.1021/jacs.2c09739

In our newest pre-print posted online today, we continue our explorations of reactions enabled by the W⁰/W^II redox manifold and report the discovery of a mild method for selectively isomerizing γ,δ-unsaturated amides into their β,γ-unsaturated counterparts without “over-isomerization” into conjugation. By controlling the ligand environment around the metal center, stereoselectivity can be controlled to favor either the (Z)- or the (E)-isomer. Though organometallic synthesis, we were able to shed light on some details of the reaction mechanism, highlighted by synthesis of a stable W^II(π-Allyl)(OAc) complex that can converted in situ to a W^II(π-allyl)(H) species, thereby intercepting a proposed intermediate in the catalytic cycle. Congrats to Tanner, Camile, and Raul!

For a link to the pre-print in ChemRxiv, click here: https://chemrxiv.org/engage/chemrxiv/article-details/63bfba1c741025af42ec927c

Congrats to Rancho Bernardo High School senior and Engle lab member, Anna Liu, who was selected today as a 2023 Regeneron Science Talent Search Scholars. Anna is one of only 300 awardees selected from a pool of nearly 2,000 applicants from across the United States. Anna has been a member of the Engle lab since November 2022 and has worked under the mentorship of Taeho Kang. Anna recently earned her first publication in the group (Organometallics 2023, 42, 11). We are so proud of you Anna! Congrats on your achievement!

For more information about the Regeneron STS program and a link the announcement, click here: https://www.societyforscience.org/regeneron-sts/2023-scholars/

Today we report a new strategy for alkene functionalization that can deliver two valuable products in a single step by partnering a mutually enabling oxidative difunctionalization and reductive difunctionalization, a process we term redox-paired alkene functionalization. In the reported reaction system, a single palladium(II) catalyst switches between Pd^IIX and Pd^IIAr forms during the catalytic cycle, each of which is active in the respective half-reactions. Specifically, the catalytic cycle achieves oxidative [3+2] annulation with 2-naphthols and reductive 1,2-diarylation with aryl iodides, expanding the scope and utility of both of these transformations. Congrats to all of the co-workers in this collaborative project: Hui-Qi, Tian (May), Shenghua, and Zhen; as well as Malkanthi, who performed computational studies under the joint guidance of Profs. Ken Houk (UCLA) and Peng Liu (Pittsburgh).

For a link to the pre-print in ChemRxiv, click here: https://chemrxiv.org/engage/chemrxiv/article-details/63ad635fff4651a6983afddf

This week, in collaboration with the group of Prof. Julien Vantourout of ICBMS Lyon, we report complementary methods for E– and Z-selective kinetic isomerization of terminal alkenes under nickel catalysis. The two protocols are operationally simple to perform, employ commercially available reagents, and tolerate numerous synthetically useful functional groups. Congrats to all of the co-authors: Camille, Anne, Shenghua, and Zi-Qi. The project was initiated during Camille’s stint as a visiting student in Lyon earlier this year and was then wrapped up over the past few weeks to close out 2022 on a high note.

For a link to the pre-print in ChemRxiv, click here: https://chemrxiv.org/engage/chemrxiv/article-details/63aa9d68a53ea689e3590038

The peer-reviewed version of our paper describing the synthesis and characterization of elusive post-β-C-elimination organopalladium complexes is online today in Organometallics. In this paper, we find that the combination of chelation stabilization from the 8-aminoquinoline directing auxiliary and strain-release from ring-opening of the nopol framework allows for facile β-C-elimination to yield a series of N,N,π-C palladacycle products. Congrats to Taeho, Rei, Anna, and Tanner from our group at Scripps; Yue from Prof. Peng Liu’s group at University of Pittsburgh; and Arnie, Jake, and Milan from the crystallography core at UCSD.

For a link to the manuscript in Organometallics, click here: https://pubs.acs.org/doi/10.1021/acs.organomet.2c00530

As a reminder, a pre-print describing this work appeared at the end of October: https://chemrxiv.org/engage/chemrxiv/article-details/635875afca86b8d57fc36848

As per tradition, we celebrated the end of the year in style with tasty food, a fun white elephant gift exchange, and great company. Johny stole the show fashion-wise with his llama-themed sweater, and the burrito blanket was the hottest gift of the lot. Wishing everyone a magical holiday seasons, and looking forward to another great year to come in 2023!

The final version of our manuscript describing the development of a toolkit of bench-stable Ni(0) precatalysts for diverse organic transformations is now in press in Angewandte Chemie. This toolkit enables reactions reliant on air-stable Ni(0) sources such as Ni(COD)₂ to be performed without an inert atmosphere glovebox using standard Schleck techniques, offering a path forward for commercial scale-up of such catalytic methods. This work was made possible through a large network of collaborators at Scripps Research, USCD, Cornell, and Bristol Myers Squibb.

For coverage of this work in C&E News, see: https://cen.acs.org/acs-news/acs-meeting-news/Nickel-tamed-reagent-toolkit/100/i11

For a link to the paper in Angewandte Chemie, click here: https://onlinelibrary.wiley.com/doi/10.1002/anie.202211794

As a reminder, a pre-print of this work was uploaded to ChemRxiv back in February: https://onlinelibrary.wiley.com/doi/10.1002/anie.202214153

Janine Abuyuan, a Master’s degree student at UCSD joins the group for an internship! At UCSD, Janine works in the group of Prof. Cliff Kubiak, and previously she completed her undergraduate degree at Barnard College, during which time she worked with Prof. Jack Norton at Columbia University. Welcome to the group, Janine!