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DOE OSTI · 3024747

B -Alkyl-borabicyclo[3.3.1]nonane Reagents Promote Closed-Shell Nickel-Catalyzed Alkylarylation Toward Encoded Cyclooctene Monomers

Ravn, Anne K. [The Scripps Research Inst., La Jolla, CA (United States)] (ORCID:0000000270403230)·Bangerter, Aimee L. [The Scripps Research Inst., La Jolla, CA (United States)]·Wagner, Ethan M. [Georgia Institute of Technology, Atlanta, GA (United States)]·Li, Shijia [Univ. of Pittsburgh, PA (United States)]·Rubel, Camille Z. [The Scripps Research Inst., La Jolla, CA (United States)] (ORCID:0000000308616590)·Wisniewski, Steven R. [Bristol Myers Squibb, New Brunswick, NJ (United States)] (ORCID:0000000160354394)·Liu, Peng [Univ. of Pittsburgh, PA (United States)] (ORCID:000000028188632X)·Gutekunst, Will. R. [Georgia Institute of Technology, Atlanta, GA (United States)] (ORCID:0000000224274431)·Engle, Keary M. [The Scripps Research Inst., La Jolla, CA (United States)] (ORCID:0000000327676556)
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Abstract

Access to new tailored monomers is essential to explore unprecedented polymer structures and modulate their properties. In previous work, we disclosed an iteroselective diarylation of 1,5-cyclooctadiene as an attractive platform for preparing diverse cyclooctene monomers; however, it was limited to C(sp 2 ) coupling partners. Established difunctionalization methods with C(sp 3 ) fragments rely on carbon-based radical formation, which is incompatible with 1,5-cyclooctadiene. This work describes a two-electron redox manifold for the nickel-catalyzed alkylarylation of 1,5-cyclooctadiene and discloses B -alkyl-borabicyclo[3.3.1]nonane (alkyl-9-BBN) as an effective transmetalating reagent for maintaining a polar reaction mechanism. The method provides 5,6-alkylarylated cyclooctenes suitable for ring-opening metathesis polymerization to obtain new materials. The properties of these polymers are benchmarked and fine-tuned by variation of coupling partners in the nickel catalysis. Density functional theory calculations revealed that destabilization of the pretransmetalation complex promotes the reactivity of alkyl-9-BBN in transmetalation compared to alkylboronic esters.

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Ravn, Anne K. [The Scripps Research Inst., La Jolla, CA (United States)] (ORCID:0000000270403230), Bangerter, Aimee L. [The Scripps Research Inst., La Jolla, CA (United States)], Wagner, Ethan M. [Georgia Institute of Technology, Atlanta, GA (United States)], Li, Shijia [Univ. of Pittsburgh, PA (United States)], Rubel, Camille Z. [The Scripps Research Inst., La Jolla, CA (United States)] (ORCID:0000000308616590), Wisniewski, Steven R. [Bristol Myers Squibb, New Brunswick, NJ (United States)] (ORCID:0000000160354394), Liu, Peng [Univ. of Pittsburgh, PA (United States)] (ORCID:000000028188632X), Gutekunst, Will. R. [Georgia Institute of Technology, Atlanta, GA (United States)] (ORCID:0000000224274431), Engle, Keary M. [The Scripps Research Inst., La Jolla, CA (United States)] (ORCID:0000000327676556). 2026-02-19. B -Alkyl-borabicyclo[3.3.1]nonane Reagents Promote Closed-Shell Nickel-Catalyzed Alkylarylation Toward Encoded Cyclooctene Monomers. https://doi.org/10.1021/acscentsci.5c02173

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