Nickel-Catalyzed O-Arylation of Primary or Secondary Aliphatic Alcohols with (Hetero)aryl Chlorides: A Comparison of Ni(I) and Ni(II) Precatalysts

Kathleen M Morrison; Nicholas J Roberts; Samantha L Dudra; Joseph P Tassone; Michael J Ferguson; Erin R Johnson; Mark Stradiotto

doi:10.1021/acs.joc.3c01584

Nickel-Catalyzed O-Arylation of Primary or Secondary Aliphatic Alcohols with (Hetero)aryl Chlorides: A Comparison of Ni(I) and Ni(II) Precatalysts

J Org Chem. 2023 Dec 13. doi: 10.1021/acs.joc.3c01584. Online ahead of print.

Authors

Kathleen M Morrison¹, Nicholas J Roberts¹, Samantha L Dudra¹, Joseph P Tassone¹, Michael J Ferguson², Erin R Johnson¹, Mark Stradiotto¹

Affiliations

¹ Department of Chemistry, Dalhousie University, 6274 Coburg Road, Halifax, Nova Scotia B3H 4R2, Canada.
² X-ray Crystallography Laboratory, Department of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2, Canada.

PMID: 38091599
DOI: 10.1021/acs.joc.3c01584

Abstract

A comparative experimental and computational study examining the interplay of the ancillary ligand structure and Ni oxidation state in the Ni-catalyzed C(sp²)-O cross-coupling of (hetero)aryl chlorides and primary or secondary aliphatic alcohols is presented, focusing on PAd-DalPhos (L1)-, CyPAd-DalPhos (L2)-, PAd2-DalPhos (L3)-, and DPPF (L4)-ligated [(L)NiCl]_n (n = 1 or 2) and (L)Ni(o-tol)Cl precatalysts. Both L1 and L2 were found to outperform the other ligands examined, with the latter proving to be superior overall. While Ni(II) precatalysts generally outperformed Ni(I) species, in some instances the catalytic abilities of Ni(I) precatalysts were competitive with those of Ni(II). Density-functional theory calculations indicate the favorability of a Ni(0)/Ni(II) catalytic cycle featuring turnover-limiting C-O bond reductive elimination over a Ni(I)/Ni(III) cycle involving turnover-limiting C-Cl oxidative addition.