Fig. 3. The range of products accessible by reductive olefin hydroalkylation.

The protocol is compatible with both primary and secondary alkyl halides bearing Brønsted/Lewis acidic and basic functionalities, including those derived from complex bioactive molecules. Both mono- and 1,2-disubstituted alkenyl amides are tolerated in the catalytic system. For 9w, the reaction was conducted with neopentyl bromide (3 equiv.) and isopropyl bromide (1.2 equiv.) using NiI₂ as the catalyst. For 9ac and 9af, reactions were conducted using iodides (X = I). For 9ad, 9ae, and 9ag, reactions were conducted using bromides (X = Br). For 9j, ~20% of an inseparable hydrodeiodination side product was detected. For 9m, ~3% of an inseparable self-coupling side product of iodide substrate was detected. 9g, 9i, 9u, 9ab, and 9af were obtained as 88:12, 93:7, 92:8, 90:10, and 91:9 regioisomeric mixtures, respectively. 9l and 9z were obtained as 5:1 and 1:1 diastereomeric mixtures, respectively. Regioisomeric and diastereomeric ratios were determined by ¹H NMR analysis. Yields are for isolated and purified products. R, functional group; X, halide; NMP, N-methyl-2-pyrrolidone; Boc, tert-butoxycarbonyl.