The use of alcohols and unsaturated reactants for the redox‐triggered generation of nucleophile–electrophile pairs represents a broad, new approach to carbonyl addition chemistry. Discrete redox manipulations that are often required for the generation of carbonyl electrophiles and premetalated carbon‐centered nucleophiles are thus avoided. Based on this concept, a broad, new family of enantioselective CC coupling reactions that are catalyzed by iridium or ruthenium complexes have been developed, which are summarized in this Minireview.

The iridium‐catalyzed, protecting group‐free synthesis of 4‐hydroxy‐2,6‐cis‐ or trans‐pyrans through successive nucleophilic and electrophilic allylations of chiral 1,3‐diols occurs with complete levels of catalyst‐directed diastereoselectivity in the absence of protecting groups, premetallated reagents, or discrete alcohol‐to‐aldehyde redox reactions.

Enantiomerically enriched potassium β-trifluoroboratoamides were synthesized as air stable solids in greater than 95:5 dr using pseudoephedrine as the chiral auxiliary. With these chiral nucleophiles, Suzuki-Miyaura cross-coupling reactions were carried out with various aryl- and hetaryl chlorides in good to excellent yields. Moreover the diastereoselectivities were preserved throughout the Suzuki–Miyaura cross-coupling reactions.

Potassium Boc-protected aminomethyltrifluoroborate, a primary aminomethyl equivalent, was synthesized successfully through a “one-pot” process. With this trifluoroborate, Suzuki–Miyaura cross-coupling reactions were investigated with a variety of both aryl- and hetaryl chlorides in good to excellent yields.

Diverse hydrogen-mediated C-C couplings enable construction of the actin-binding marine polyketide swinholide A in only 15 steps (LLS); roughly half the steps required in two prior total syntheses. The redox-economy, chemo- and stereoselectivity embodied by this new class of C-C couplings are shown to evoke a step-change in efficiency.

Seven potassium Boc-protected secondary aminomethyltrifluoroborates were prepared in a standardized two step process. The Suzuki–Miyaura cross-coupling reaction was studied with this new class of nucleophiles, and a large variety of aryl and hetaryl chlorides provided the desired products in good to excellent yields, thereby allowing easy access to secondary aminomethyl substructures.

Sulfamates were studied as the electrophilic partners in the palladium-catalyzed Suzuki–Miyaura cross-coupling reaction with potassium Boc-protected primary and secondary aminomethyltrifluoroborates. A broad range of substrates was successfully coupled to provide the desired products. Complex molecules containing a new carbon-carbon bond and an aminomethyl moiety could be prepared through this developed method.

Acylsilanes have been utilized in various transformations for synthesis of functionalized organosilicon derivatives due to their importance in medicinal- and materials science. This review summarizes recent photo-induced reactions of acylsilanes,...