Nitroalkane Addition to Unactivated Alkenes – Manuscript in Press at ACS Catalysis

Our recent study describing the palladium(II)-catalyzed coupling of nitroalkanes and unactivated alkenes has been accepted and appears online today in ACS Catalysis. We describe how the combination of PdI2 as catalyst and HFIP as solvent is uniquely effective in enabling this historically challenging coupling process. The method allows for simple readily accessible starting materials to be elaborated into densely functionalized nitroalkane products, which can then be further derivatized as desired. Teaming up with our computational collaborators from the Liu group at the University of Pittsburgh, we describe how the carbopalladation transition state is stabilized by a Na···I interaction and an H···I hydrogen bond with HFIP. Congrats to Amit, Por, Hui-Qi, and John from our group; and Turki and Binh from the Liu group on this study.

To read the peer-reviewed paper in ACS Catalysis, click here:

As a reminder, a pre-print describing this transformation first appeared in ChemRxiv back in February:

Enantioselective Ni-Catalyzed Dicarbofunctionalization – Now in Press at JACS

Today’s second paper from the group appears in the Journal of the American Chemical Society and describes the first enantioselective nickel-catalyzed 1,2-dicarbofunctionalization of unactivated alkenes involving a closed-shell pathway. Key to the success of the transformation is the combined use of a sterically bulky monodentate sulfonamide directing group and a chiral hemi-labile bioxazoline (Bn-biOx) ligand, which work together during enantiodetermining arylnickel migratory insertion. This was a massive undertaking that spanned three years and involved collaborators from Scripps (Omar, Taeho, Pranali, Camille, Joe, Brittany, Quynh, Emily, and Jason), University of Pittsburgh (Turki), and Bristol Myers Squibb (Steve). Congrats to everyone on a great team effort!

Click here for a link to the paper in J. Am. Chem. Soc.:

As a reminder, an initial pre-print describing this work first appeared in ChemRxiv back in June:

Palladium-catalyzed 1,2-carbofluorination paper – In Press at Angewandte Chemie

In the first of two papers appearing in final peer-reviewed form today, we report a new method for 1,2-carbofluorination of unactivated alkenes under Pd(II)/Pd(IV) catalysis in Angewandte Chemie International Edition. This new method is enabled by a unique sterically bulky gem-diethyl pyridyl amine directing group that coordinates to the palladium(II) catalyst in a bidentate fashion, controlling the regioselectivity of migratory insertion and promoting C(sp3)–F reductive elimination. The method can tolerate different substitution patterns of the alkene as well as a broad scope of aryl- and alkenylboron coupling partners. Congrats to entire team: Zhonglin, Luke, Juntao, Zi-Qi, and Nana from Scripps; and Geraint from BMS Discovery Chemistry.

For a link to the paper in Angewandte Chemie International Edition, click here:

As a reminder, this work was first described in a ChemRxiv pre-print back in April:

Wishing you the best Por!

Today we bid farewell to Warabhorn (Por) Rodphon, who has finished her full-year internship in our lab. We were very happy to be able to give Por a proper send off, including a ramen trip! Best of luck in your next adventure and we can’t wait to see all of your accomplishments! We miss you already!