The ability to understand and predict reactivity is essential for the development of new reactions. In the context of Ni-catalyzed C­(sp3)–O functionalization, we have developed a unique strategy employing activated cyclopropanols to aid the design and optimization of a redox-active leaving group for C­(sp3)–O arylation. In this chemistry, the cyclopropane ring acts as a reporter of leaving-group reactivity, since the ring-opened product is obtained under polar (2e) conditions, and the ring-closed product is obtained under radical (1e) conditions. Mechanistic studies demonstrate that the optimal leaving group is redox-active and are consistent with a Ni­(I)/Ni­(III) catalytic cycle. The optimized reaction conditions are also used to synthesize a number of arylcyclopropanes, which are valuable pharmaceutical motifs.

A Negishi cross-coupling of α-hydroxy ester derivatives and arylzinc reagents has been developed. This reaction tolerates both primary and secondary C(sp 3 )−O alcohol precursors and achieves efficient cross-coupling under Ni catalysis without the need for added external metal reductant, photocatalyst, or additives. The arylation of readily accessible C(sp 3 )−O electrophiles in this operationally simple, rapid, and mild reaction provides a complementary way of accessing desirable α-aryl ester products.

A Ni-catalyzed cross-coupling of readily accessible O-alkyl xanthate esters or thiocarbonyl imidazolides and organozinc reagents for the synthesis of thiocarboxylic acid derivatives has been developed. This method benefits from a fast reaction time, mild reaction conditions, and ease of starting material synthesis. The use of transition-metal catalysis to access a diverse range of thiocarbonyl-containing compounds provides a useful complementary approach when compared with previously established methodologies.

Herein, we describe a protocol for the ring-opening arylation of 1-arylcyclopropyl tosylates, in which boronic acids promote ring-opening and a Ni catalyst facilitates arylation in high regioselectivity. A number of...