Directed Cyclization Paper – Now In Press in Chem. Sci.

Xin, Zi-Qi, and Binh’s paper describing substrate-directed, palladium(II)-catalyzed intramolecular hydrofunctionalization has been accepted for publication in Chem. Sci. In this investigation we demonstrate that an bidentate AQ-amide directing group is able to promote otherwise disfavored ring-closure pathways, including those disfavored by Baldwin’s rules (e.g., 5-endotrig). This marks the culmination of a four-year journey initiated by former high-school intern Jessica (now at MIT) and her mentor John (now at Bristol Myers Squibb). Congratulations are in order for all co-authors for getting this to the finish line: Xin, Zi-Qi, John, Jessica, Van, Hui-Qi, Zhen, Zhonglin, and Kin from Scripps Research; Binh and Peng from University of Pittsburgh; and Rong (and Xin) from Nankai University Medical School.

For a link to the paper, click here: https://pubs.rsc.org/en/content/articlelanding/2020/sc/d0sc03409f#!divAbstract

This work was first described in April in a pre-print that was deposited on ChemRxivhttps://chemrxiv.org/articles/Controlling_Cyclization_Pathways_in_Palladium_II_-Catalyzed_Intramolecular_Alkene_Hydrofunctionalization_via_Substrate_Directivity/12090402/1

Regiodiverent Alkene Hydroarylation Paper Accepted in Angew. Chem. Int. Ed.

Our recent project in collaboration with the Liu lab from the University of Pittsburgh on the regiodivergent hydroarylation/-alkenylation of alkenyl carboxylic acids with organoboronic acids has been accepted in Angew. Chem. Int. Ed. and appears in final form online this week. Key to the success of this methodology is the discovery of a novel 4,4-dibenzyl-Pyrox ligand that grants access to the anti-Markovnikov product, overriding the inherent selectivity for the Markovnikov product under ligand-free conditions. Mechanistic studies point to a unique carboxylate-mediated concerted hydronickelation mechanism. Congrats to Engle lab members Zi-Qi, Ruohan, Van, and Yang; as well as a Liu lab member Yue.

For a link to the paper, click here: https://onlinelibrary.wiley.com/doi/10.1002/anie.202010840

This work was first described in July in a pre-print that was deposited on ChemRxiv: https://chemrxiv.org/articles/Ligand-Controlled_Regiodivergence_in_Nickel-Catalyzed_Hydroarylation_and_Hydroalkenylation_of_Alkenyl_Carboxylic_Acids/12650009