Transition‐Metal‐Catalyzed Sequential Cross‐Coupling of Bis(iodozincio)methane and ‐ethane with Two Different Organic Halides

Abstract

Bis(iodozincio)methane, prepared from diiodomethane and zinc, reacts with an organic halide in the presence of a transition-metal catalyst to give an iodozinciomethylenated compound; this then reacts with another organic halide to form a C--C bond. The overall process connects two electrophiles with one carbon atom. Bis(iodozincio)ethane can also undergo this transformation, yielding a new stereogenic center. The asymmetric induction of this stereogenic center was investigated by using a chiral palladium catalyst.

Diethylzinc‐Mediated Allylation of Carbonyl Compounds Catalyzed by [(NHC)(PR3)PdX2] and [(NHC)Pd(η3‐allyl)Cl] Complexes

“…Elemental analyses were performed at the ICSN (microanalytical service). Compounds 14a, [35,36] 14b, [36] 17a, [7f] 17b, [7f,37] 17c, [7f,12g,38] 17d, [12g] 17f, [12g] 17h, [38] 17i, [39] 17j, [40] 17k, [12f] 17l, [41] 18k, [12f] 20c, [42] 20e, [43] 20f, [37] 20i, [43,44] 20j, [42,35b] and 20k [35b] have previously been described in the literature. 0.088 mmol).…”

Carbon–Carbon Bond Forming Reactions Mediated by Organozinc Reagents

“…in THF at rt (Scheme 4.92) [286]. Only one carbon-zinc bond reacts under these conditions, thus leading to styrylzinc iodide 397 suitable for a second carbon-carbon-bond-forming reaction.…”

1,4‐Addition of Bis(iodozincio)methane to α,β‐Unsaturated Ketones: Chemical and Theoretical/Computational Studies

“…When these two nucleophilic attacks occur in a stepwise manner, the first reaction can be regarded as a zinciomethylation reaction. [4] In fact, we previously reported sequential coupling of 1 with organic halides: [5] The first coupling reaction of 1 with an organic halide affords the organozinc compound, which then undergoes a further cross-coupling reaction. Similarly, 1,4addition of 1 to a,b-unsaturated ketones would be another possible approach to the introduction of the iodozinciomethyl group into organic compounds.…”