Abstract 1,2‐Bis‐boronic esters are useful synthetic intermediates particularly as the two boronic esters can be selectively functionalized. Usually, the less hindered primary boronic ester reacts, but herein, we report a coupling reaction that enables the reversal of this selectivity. This is achieved through the formation of a boronate complex with an electron‐rich aryllithium which, in the presence of an electron‐deficient aryl nitrile, leads to the formation of an electron donor–acceptor complex. Following visible‐light photoinduced electron transfer, a primary radical is generated which isomerizes to the more stable secondary radical before radical‐radical coupling with the arene radical‐anion, giving β‐aryl primary boronic ester products. The reactions proceed under catalyst‐free conditions. This method also allows stereodivergent coupling of cyclic cis‐1,2‐bis‐boronic esters to provide trans‐substituted products, complementing the selectivity observed in the Suzuki–Miyaura reaction.

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Selective Coupling of 1,2‐Bis‐Boronic Esters at the more Substituted Site through Visible‐Light Activation of Electron Donor–Acceptor Complexes

We disclosed a regio-selective C-H and N-H bond functionalization of indolines using alcohols in water via tandem dehydrogenation of N-heterocycles and alcohols. A diverse range of N- and C3-alkylated indolines/indoles were accessed utilizing a new cooperative iridium catalyst. The practical applicability of this methodology was demonstrated by the preparative-scale synthesis and synthesis of a psychoactive drug, N,N-dimethyltryptamine. A catalytic cycle is proposed based on several kinetic experiments, series of control experiments and density functional theory calculations.

Regio-Selective C3- and N-Alkylation of Indolines in Water under Air Using Alcohols.

Visible Light-Promoted Magnesium, Iron, and Nickel Catalysis Enabling C(sp3)-H Lactonization of 2-Alkylbenzoic Acids.

The radical cations of tertiary amines (R3N) have been well-established as the precursors of HAT reagents in photochemical transformations. Similarly, thiols and thioacids bearing SH groups have also been widely applied as HAT reagents. Despite the fact that sulfoxides (R2SO) and sulfides (RSR) also bear lone pairs of electrons, these compounds have been barely reported as HAT reagents in photocatalysis. On the other hand, the α-C–H 4-pyridylation of O or N-containing compounds has been documented, whereas 2-pyridylation remains challenging. However, the antihistamine and anticholinergic agent carbinoxamine is an ether bearing 2-pyridyl, which has not been obtained by the existing α-photoarylation of ether. In this work, we report the discovery of a non-donor–acceptor (D–A) type organic photoreductant CBZ6 and sulfoxide/sulfide synergistically catalyzed general α-C(sp3)–H arylation of ethers, thioethers and amines. By using as low as 1 mol% of CBZ6 as a recyclable organic photoreductant and sulfoxides or sulfides as a new type of HAT reagent, the 2- or 4-pyridylation of O, N, or S-containing compounds has been accomplished. This is the first base-free version of α-C–H 2-/4-pyridylation of O, N, or S-containing compounds. It is the first example of sulfoxides or sulfides working as HAT reagents. It is also the first general method for photocatalytic HAT 2-pyridylation of various ethers, amines or thioethers.

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Synthesis of carbinoxamine via α-C(sp3)–H 2-pyridylation of O, S or N-containing compounds enabled by non-D–A-type super organoreductants and sulfoxide- or sulfide HAT reagents

An efficient and convenient method to synthesize 6-oxyalkylated 1,2,4-triazine-3,5(2H, 4H)-diones has been developed via visible-light-induced cross-dehydrogenative coupling reaction between 1,2,4-triazine-3,5(2H, 4H)-diones and ethers with a wide range of functional group tolerance. The present transformation employs the cheap and low-toxic 2-tert-butylanthraquinone as a metal-free photocatalyst and air as a green oxidant at room temperature. Moreover, this reaction can also be driven by sunlight as a clean energy resource. The synthetic utility of this method is further demonstrated by gram-scale reaction and application in the preparation of key intermediates of bioactive molecules.

Chang Xu

Papers

Visible-Light-Induced α-Amino C–H Bond Arylation Enabled by Electron Donor–Acceptor Complexes