We report herein a new method for the photoredox activation of boronic esters. Using these reagents, an efficient and high‐throughput continuous flow process was developed to perform a dual iridium‐ and nickel‐catalyzed C(sp2)–C(sp3) coupling by circumventing solubility issues associated with potassium trifluoroborate salts. Formation of an adduct with a pyridine‐derived Lewis base was found to be essential for the photoredox activation of the boronic esters. Based on these results we were able to develop a further simplified visible light mediated C(sp2)–C(sp3) coupling method using boronic esters and cyano heteroarenes under flow conditions.

Leucinol and valinol have been identified as efficient organocatalysts for the aldol reaction of isatin and its derivatives (as examples of activated, non-enolizable ketones) with acetone. Uncommon mechanistic features were observed and used in the formulation of the transition state of the reaction.

An expedient synthesis of the indole alkaloid nazlinine is reported. Judicious choice of flow electrochemistry as an enabling technology has permitted the rapid generation of a small library of unnatural relatives of this biologically active molecule. Furthermore, by conducting the key electrochemical Shono oxidation in a flow cell, the loading of electrolyte can be significantly reduced to 20 mol % while maintaining a stable, broadly applicable process.

A mild, simple oxidation protocol employing ironA C H T U N G T R E N N U N G (III) chloride as a catalyst and hydrogen peroxide as a stoichiometric oxidant was found to be compatible with an intramolecular carbonyl nitroso ene reaction and allowed us to efficiently convert hydroxamic acids into a diverse range of 1,2-and 1,3-amino alcohol derivatives in a single operation.

A new, highly efficient Lewis base catalyst for a practical enantio‐ and diastereoselective crotylation of unsaturated aldehydes with E‐ and Z‐crotyltrichlorosilanes has been developed. The method was employed as a key step in a novel asymmetric synthesis of bioactive serrulatane diterpene (−)‐elisabethadione. Other strategic reactions for setting up the stereogenic centers included anionic oxy‐Cope rearrangement and cationic cyclization. The synthetic route relies on simple, high yielding reactions and avoids use of protecting groups or chiral auxiliaries.

We have found that ligand control over the carbon-carbon and carbon-heteroatom bond formation on the nickel center provides an easy and convenient route to symmetrical (minor) and unsymmetrical (major) isomers of sulfur-and selenium-substituted 1,3-dienes. The unsymmetrical product is a new type of 1,4-substituted conjugated diene, which was readily synthesized from alkynes and diaryldichalcogenides. The unique feature of this developed one-pot transformation is total stereodefined synthesis of the diene skeleton, controlling not only the configuration of the double bond but also the s-gauche conformation of the central C-C bond. The mechanistic study revealed the key feature of alkyne insertion into the Ni-E and Ni-C bonds (E ) S, Se), which governs the direction of the chemical transformation.

A range of heterocycles, namely thiazoles, imidazoles, imidazopyridines, thiazolidines and dimethoxyindoles, have been synthesised directly from alkenes via a two-step ketoidoination/cyclisation protocol. The alkene starting materials are themselves readily accessible using many different and well-established approaches, and allow access to a variety of heterocycles with excellent yields and regioselectivity.

A continuous‐flow synthesis of aziridines by palladium‐catalyzed C(sp3)−H activation is described. The new flow reaction could be combined with an aziridine‐ring‐opening reaction to give highly functionalized aliphatic amines through a consecutive process. A predictive mechanistic model was developed and used to design the C−H activation flow process and illustrates an approach towards first‐principles design based on novel catalytic reactions.