Continuing with our recent theme of developing new methods for C(sp³)–S bond formation via nickel-catalyzed syn-carbosulfenyation of alkenes, in today’s ChemRxiv pre-print we describe a new three-component method for combining alkylzinc nucleophiles, sulfur electrophiles, and unactivated alkenes. The method complements previous methodology from our group by expanding the scope of C(sp²) nucleophiles to C(sp³) nucleophiles and is enabled by use a bidentate directing auxiliary group. The method is compatible with a diverse collection of coupling partners including various E– and Z-configured internal alkenes. Congrats to the project team, grad students Zi-Qi and Hui-Qi and visiting undergrad Wen-Ji. Great work team!

For a link to the pre-print in ChemRxiv, click here: https://chemrxiv.org/engage/chemrxiv/article-details/6233b0c08ab3732b56687bad

The final version of our paper on free-amine-directed 1,2-carboamination of alkenes under nickel catalysis is available online today in ACS Catalysis. In this manuscript, we describe how careful tuning of the reactivity of the nitrogen electrophile through modification of the leaving group allows for the first example of three-component 1,2-difunctionalization of alkene with a free amine directing group. The reaction proceeds with a broad scope of organoboron coupling partners, cyclic and acyclic amine electrophiles, and primary and secondary alkenyl amine substrates. Congrats to Taeho, José, and Zi-Qi, as well as our collaborators Klement and Peter from discovery chemistry at Bristol Myers Squibb.

For a link to the paper, click here: https://pubs.acs.org/doi/full/10.1021/acscatal.2c00373

As a reminder, a pre-print of the paper first appeared in ChemRxiv back in December 2021: https://chemrxiv.org/engage/chemrxiv/article-details/61b14f9a7ada95b46a6e62ee

We continue our investigations into dual catalytic alkene functionalization promoted by a metal and a transient directing group (TDG). We previously described methods for Heck-type hydroarylation and 1,2-arylfluorination. In this ChemRxiv pre-print we show that it is instead possible to achieve C(alkenyl)–H activation from a common Pd(II)–alkene olefin intermediate, as promoted by a tailored carboxylate additive. This mode of reactivity can be leveraged in the oxidative cross-coupling of two alkenes to yield 1,3-diene products, including axially chiral 3-aryl-1,3-dienes. Congrats to the entire project team: Mingyu, Juntao, Hui-Qi, and Raúl from our lab; and Tuğçe from the Liu group the University of Pittsburgh.