Silylmethyl, tertiary-alkyl, alkenyl, and aryl Grignard reagents underwent intermolecular addition to olefins, such as styrenes, conjugated dienes, and enynes under an air atmosphere to give homologated alcohols. For example, (trimethylsilyl)methylmagnesium chloride and alpha-methylstyrene in ether at room temperature under dry air directly furnished 2-phenyl-4-(trimethylsilyl)-2-butanol in good yield. As the Grignard addition to olefins under argon with rigorous exclusion of O2 did not proceed at all, the above reaction should involve a radical mechanism: an alkyl radical generated by the aerial oxidation of the Grignard reagent adds to olefin, which is followed by oxygenation. Representative examples of this transformation, where products were obtained in good to excellent diastereo- or regioselectivity, are also disclosed.

Diene for conjugate addition: Iron(II) chloride switches the reaction course of the three‐component coupling of a Grignard reagent, an alkyl halide, and a dienamide, thus making the amide a simple yet versatile chiral template.

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When an electrophile (H+ or an alkyl halide) was added to a mixture of 1-aryl-2-aza-1,3-butadiene and allyl Grignard reagent, selective assembly of the azadiene, nucleophiles, and an electrophile took place to give α,α′-diallylated amine in one pot.