Compared to Grignard reactions, this reaction is very selective towards aldehydes with large tolerance towards a range of functional groups such as ketones, esters, amides and nitriles. Enals give exclusively 1,2-addition. Solvents of choice are DMF and DMSO, one solvent requirement is solubility of the chromium salts. Nozaki–Hiyama–Kishi reaction is a useful method for preparing medium-size rings.[3]
In 1983 the scope was extended by the same authors to include vinyl halides or triflates and aryl halides.[4] It was observed that the success of the reaction depended on the source of chromium(II) chloride and in 1986 it was found that this is due to nickel impurities.[5] Since then nickel(II) chloride is used as a co-catalyst.[6]
In the same year Yoshito Kishi et al. independently discovered the beneficial effects of nickel in his quest for palytoxin:[7]
^Grignard-type carbonyl addition of allyl halides by means of chromous salt. A chemospecific synthesis of homoallyl alcohols Yoshitaka Okude, Shigeo Hirano, Tamejiro Hiyama, Hitoshi Nozaki J. Am. Chem. Soc.1977; 99(9); 3179–3181. doi:10.1021/ja00451a061
^(a) MacMillan, D. W. C.; Overman, Larry E. "Enantioselective Total Synthesis of (−)-7-Deacetoxyalcyonin Acetate. First Synthesis of a Eunicellin Diterpene" J. Am. Chem. Soc. 1995, 117 (41), 10391–10392. doi:10.1021/ja00146a028. (b) Lotesta, S. D.; Liu, J.; Yates, E. V.; Krieger, I.; Sacchettini, J. C.; Freundlich, J. S.; Sorensen, E. J. "Expanding the pleuromutilin class of antibiotics by de novo chemical synthesis" Chem. Sci. 2011, 2, 1258–1261. doi:10.1039/C1SC00116G.
^Reactions of alkenylchromium reagents prepared from alkenyl trifluoromethanesulfonates (triflates) with chromium(II) chloride under nickel catalysis K. Takai, M. Tagashira, T. Kuroda, K. Oshima, K. Utimoto, H. Nozaki J. Am. Chem. Soc.; 1986; 108(19); 6048–6050. doi:10.1021/ja00279a068
^Catalytic effect of nickel(II) chloride and palladium(II) acetate on chromium(II)-mediated coupling reaction of iodo olefins with aldehydes Haolun Jin, Junichi Uenishi, William J. Christ, Yoshito Kishi J. Am. Chem. Soc.; 1986; 108(18); 5644–5646. doi:10.1021/ja00278a057