Electrochemically Driven Deoxygenative Borylation of Alcohols and Carbonyl Compounds.

We present a new, unified approach for the transformation of benzylic and allylic alcohols, aldehydes, and ketones into boronic esters under electroreductive conditions. Key to our strategy is the use of readily available pinacolborane, which serves both as an activator and an electrophile by first generating a redox-active trialkylborate species and then delivering the desired deoxygenatively borylated product. This strategy is applicable to a variety of substrates and can be employed for the late-stage functionalization of complex molecules.

An Electrochemical Strategy to Synthesize Disilanes and Oligosilanes from Chlorosilanes.

Silanes are important compounds in industrial and synthetic chemistry. Here, we develop a general approach for the synthesis of disilanes as well as linear and cyclic oligosilanes via the reductive activation of readily available chlorosilanes. The efficient and selective generation of silyl anion intermediates, which are arduous to achieve by other means, allows for the synthesis of various novel oligosilanes by heterocoupling. In particular, this work presents a modular synthesis for a variety of functionalized cyclosilanes, which may give rise to materials with distinct properties from linear silanes but remain challenging synthetic targets. In comparison to the traditional Wurtz coupling, our method features milder conditions and improved chemoselectivity, broadening the functional groups that are compatible in oligosilane preparation. Computational studies support a mechanism whereby differential activation of sterically and electronically distinct chlorosilanes are achieved in an electrochemically driven radical-polar crossover mechanism.

A guide to troubleshooting metal sacrificial anodes for organic electrosynthesis.

The development of reductive electrosynthetic reactions is often enabled by the oxidation of a sacrificial metal anode, which charge-balances the reductive reaction of interest occurring at the cathode. The metal oxidation is frequently assumed to be straightforward and innocent relative to the chemistry of interest, but several processes can interfere with ideal sacrificial anode behavior, thereby limiting the success of reductive electrosynthetic reactions. These issues are compounded by a lack of reported observations and characterization of the anodes themselves, even when a failure at the anode is observed. Here, we weave lessons from electrochemistry, interfacial characterization, and organic synthesis to share strategies for overcoming issues related to sacrificial anodes in electrosynthesis. We highlight common but underexplored challenges with sacrificial anodes that cause reactions to fail, including detrimental side reactions between the anode or its cations and the components of the organic reaction, passivation of the anode surface by an insulating native surface film, accumulation of insulating byproducts at the anode surface during the reaction, and competitive reduction of sacrificial metal cations at the cathode. For each case, we propose experiments to diagnose and characterize the anode and explore troubleshooting strategies to overcome the challenge. We conclude by highlighting open questions in the field of sacrificial-anode-driven electrosynthesis and by indicating alternatives to traditional sacrificial anodes that could streamline reaction optimization.

Enabling Al sacrificial anodes in tetrahydrofuran electrolytes for reductive electrosynthesis.

Al0 is widely used as a sacrificial anode in organic electrosynthesis. However, there remains a notable knowledge gap in the understanding of Al anode interface chemistry under electrolysis conditions. We hypothesize that Al interfacial chemistry plays a pivotal role in the discernible bias observed in solvent selections for reductive electrosynthesis. The majority of existing methodologies that employ an Al sacrificial anode use N,N-dimethylformamide (DMF) as the preferred solvent, with only isolated examples of ethereal solvents such as tetrahydrofuran (THF). Given the crucial role of the solvent in determining the efficiency and selectivity of an organic reaction, limitations on solvent choice could significantly hinder substrate reactivity and impede the desired transformations. In this study, we aim to understand the Al metal interfaces and manipulate them to improve the performance of an Al sacrificial anode in THF-based electrolytes. We have discovered that the presence of halide ions (Cl-, Br-, I-) in the electrolyte is crucial for efficient Al stripping. By incorporating halide additive, we achieve bulk Al stripping in THF-based electrolytes and successfully improve the cell potentials of electrochemically driven reductive methodologies. This study will encourage the use of ethereal solvents in systems using Al sacrificial anodes and guide future endeavors in optimizing electrolytes for reductive electrosynthesis.

Deep Electroreductive Chemistry: Harnessing Carbon- and Silicon-based Reactive Intermediates in Organic Synthesis.

This Viewpoint outlines our recent contribution in electroreductive synthesis. Specifically, we leveraged deeply reducing potentials provided by electrochemistry to generate radical and anionic intermediates from readily available alkyl halides and chlorosilanes. Harnessing the distinct reactivities of radicals and anions, we have achieved several challenging transformations to construct C-C, C-Si, and Si-Si bonds. We highlight the mechanistic design principle that underpinned the development of each transformation and provide a view forward on future opportunities in growing area of reductive electrosynthesis.

Titanium and Cobalt Bimetallic Radical Redox Relay for the Isomerization of N-Bz Aziridines to Allylic Amides.

Herein a bimetallic radical redox-relay strategy is employed to generate alkyl radicals under mild conditions with titanium(III) catalysis and terminated via hydrogen atom transfer with cobalt(II) catalysis to enact base-free isomerizations of N-Bz aziridines to N-Bz allylic amides. This reaction provides an alternative strategy for the synthesis of allylic amides from alkenes via a three-step sequence to accomplish a formal transpositional allylic amination.

Sequential Reduction of Nitroalkanes Mediated by CS2 and Amidine/Guanidine Bases: A Controllable Nef Reaction.

In this letter, we describe a mild, functional group-tolerant reductive Nef reaction that utilizes CS2 and an amidine or guanidine base to sequentially cleave N-O bonds. These conditions transform secondary nitroalkanes to ketones via an isolable oxime with minimal erosion at labile stereogenic carbons, show excellent compatibility with groups sensitive to oxidizing or reducing conditions, display good scalability, and are well-suited for generating useful 3-pyrrolidinone motifs from readily accessible 1,3-dipolar cycloaddition products.