Novartis has selected Keary as the recipient of the 2019 Early Career Award in Chemistry in recognition of the Engle lab’s contributions to catalytic alkene functionalization. This award provides two years of unrestricted funding to explore new research directions. Bravo, Keary and the Engle lab team!
The 2019 Engle Lab Holiday Party is in the books, featuring diverse and delicious foods from fried chicken to tamales, a spirited white elephant gift exchange, and boardgames galore. The party also doubled as a send-off for Joe, who recently defended his Ph.D. and will start 2020 in Pasadena in the lab of Prof. Jonas Peters. Congrats, Joe!
Happy holidays from our lab family to yours, and here’s to a great 2020!
Appearing online this week in Nature Catalysis, our De-Wei, Yang, and team describe an unusual CuH-catalyzed cascade reaction to transform terminal alkynes into enaptioenriched 1,1-aminoboron compounds in a single step. In addition to synthetic applications of this remarkable transformation, we examined its mechanistic underpinnings to understand the origins of reactivity and selectivity. Thanks to Huiling from Prof. Peng Liu’s group at the University of Pittsburgh for a great collaboration and our colleagues Jason and Brittany from the Automated Synthesis Facility at Scripps Research. In case anyone missed it, a pre-print of this work was deposited in ChemRxiv back in April (click here).
Click here for a link to the paper: https://www.nature.com/articles/s41929-019-0384-6
Congrats to Van, Sri, and Mingyu, whose review article entitled, “Recent Applications of Chiral Phosphoric Acids in Palladium Catalysis,” has been accepted for publication in Org. Biomol. Chem. The article provides an overview of key reaction classes as well as different modes of co-catalysis that have emerged in this area during the past decade.
For a link to the paper, click here: https://pubs.rsc.org/en/content/articlelanding/2019/ob/c9ob02205h#!divAbstract
For the past few years, our group has developed a toolkit of catalytic alkene 1,2-difunctionalization reactions using a substrate directivity strategy. Our early work employed bi- and tridentate auxiliaries for this purpose, which have proven to be highly effective and generally useful. Recently, in an exciting series of studies, we have found that simple functional groups are also capable of directing nickel-catalyzed 1,2-diarylation. In the present paper, as part of our ongoing collaboration with Bristol-Myers Squibb, Joe, Taeho, Van, Steve (from BMS Process Chemistry), Malkanthi, Tanner, and Kane describe the use of simple carboxylic acids as competent directing groups for alkene functionalization. After 1,2-diarylation, we can take advantage of classical and modern carboxylic acid functional group interconversions to access a myriad of 1,2,3-trifunctinoalized core structures. Nice work to all of the authors, and special congratulations to our former high school intern Kane, for publishing his first paper!
For a link to the paper, click here: https://onlinelibrary.wiley.com/doi/abs/10.1002/ange.201913062
Our most recent collaboration with Pfizer and the Liu group at the University of Pittsburgh is now in press at ACS Catalysis. Methods to access small carbo- and heterocycles are of special importance in modern pre-clinical drug discovery and development owing the special properties of such motifs (conformationally restricted, low lipophilicity, etc.). In this project we developed a method to access substituted cyclopropyl boronic esters from benzylidene cyclopropanes (BCPs), which in turn can be made in a single step from benzaldehydes. While optimizing the reaction, we discovered an interesting effect of the ligand structure on pathway selectivity, and ultimately identified one ligand (BINAP) that could give almost exclusively ring-closed products, and another (dppe) that could give almost exclusively ring-opened products. To shed light on this phenomenon, our collaborators in the Liu group built a computational model that explains the observed reactivity trends. In terms of practical utility, we found the reaction to be compatible with a wide variety of azaheterocycles that are typically challenging to use in catalysis but are essential for medicinal chemists. Congratulation to all authors, particularly project co-leads Jose and Taeho.
For a link to the paper, click here: https://pubs.acs.org/doi/10.1021/acscatal.9b03557