Despite the enormous research efforts in recent years regarding lignin depolymerisation and functionalisation, few commercial products are available. This review provides a summary and viewpoint of extensive research in the lignin-to-product valorisation chain, with an emphasis on downstream processing of lignin derived feedstock into end products. It starts with an introduction of available platform chemicals and polymeric derivatives generated from lignin via existing depolymerisation and functionalisation technologies. Following that, detailed analyses of various strategies for the downstream processing of lignin derived platform chemicals and materials into fuels, valued-added chemicals and functional polymers are provided. A concise techno-economic analysis of various downstream processes is conducted based on the market demand of the end product, economic potential and technological readiness, enabling the identification of processes that are potentially both economically competitive and commercially feasible, and shedding light on processes which deserve further technological development. We wish this review will stimulate further advances in the sustainable production of value-added products from lignin to integrate this invaluable “bio-waste” into the chemical/materials supply chain.

Downstream processing of lignin derived feedstock into end products.

Can organic chemistry mimic nature in efficiency and sustainability? Not yet, but recent developments in photoredox catalysis animated the synthetic chemistry field, providing greener opportunities for industry and academia.

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Chemistry glows green with photoredox catalysis.

Cross-coupling reaction between two C–H bonds has become a fundamental strategy in synthetic organic chemistry. With its increasing importance in green chemistry, atom economy, and step economy, it...

En Route to Intermolecular Cross-Dehydrogenative Coupling Reactions.

Electrochemistry offers opportunities to promote single-electron transfer (SET) redox-neutral chemistries similar to those recently discovered using visible-light photocatalysis but without the use of an expensive photocatalyst. Herein, we introduce a microfluidic redox-neutral electrochemistry (μRN-eChem) platform that has broad applicability to SET chemistry, including radical-radical cross-coupling, Minisci-type reactions, and nickel-catalyzed C(sp2)-O cross-coupling. The cathode and anode simultaneously generate the corresponding reactive intermediates, and selective transformation is facilitated by the rapid molecular diffusion across a microfluidic channel that outpaces the decomposition of the intermediates. μRN-eChem was shown to enable a two-step gram-scale electrosynthesis of a nematic liquid crystal compound, demonstrating its practicality.

Microfluidic electrochemistry for single-electron transfer redox-neutral reactions.

Despite their impressive capacity to access diverse functional groups and to synthesize structurally complex molecules, the majority of the organic reactions suffers from harsh conditions, low atom economy, and hazardous waste production. The goal of our research is geared towards developing efficient methods to minimize the adverse environmental impact and contributing to chemical sustainability. Herein, we illustrate three distinct green approaches, studying the novel reactivities with environmentally innocuous reagents to improve the synthetic efficiency, utilization of natural feedstocks, and employment of green energy to facilitate various important chemical transformations. From this perspective article, we hope to provide an overview of green synthetic chemistry and inspire the expansion of the field in the future.

Perspectives on green synthesis and catalysis

Minisci alkylation is of prime importance for its applicability in functionalizing diverse heteroarenes, which are core structures in many bioactive compounds. In alkyl radical generation processes, precious metal catalysts, high temperatures and excessive oxidants are generally involved, which lead to sustainability and safety concerns. Herein we report a new strategy using diacetyl (2,3-butanedione) as an abundant, visible light-sensitive and “traceless” hydrogen atom abstractor to achieve metal-free cross-dehydrogenative Minisci alkylation under mild conditions. Mechanistic studies supported hydrogen atom transfer (HAT) between an activated C(sp3)–H substrate and diacetyl. Moreover, with the assistance of di-tert-butyl peroxide (DTBP), the scope of the reaction could be extended to strong aliphatic C–H bonds via diacetyl-mediated energy transfer. The robustness of this strategy was demonstrated by functionalizing complex molecules such as quinine, fasudil, nicotine, menthol and alanine derivatives.

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Diacetyl as a “traceless” visible light photosensitizer in metal-free cross-dehydrogenative coupling reactions

Transition-metal-catalyzed cross-couplings to construct C-C, C-O, and C-N bonds have revolutionized chemical science. Despite great achievements, these metal catalysts also raise certain issues including their high cost, requirement of specialized ligands, sensitivity to air and moisture, and so-called "transition-metal-residue issue". Complementary strategy, which does not rely on the well-established oxidative addition, transmetalation, and reductive elimination mechanistic paradigm, would potentially eliminate all of these metal-related issues. Herein, we show that aryl triflates can be coupled with potassium aryl trifluoroborates, aliphatic alcohols, and nitriles without the assistance of metal catalysts empowered by photoenergy. Control experiments reveal that among all common aryl electrophiles only aryl triflates are competent in these couplings whereas aryl iodides and bromides cannot serve as the coupling partners. DFT calculation reveals that once converted to the aryl radical cation, aryl triflate would be more favorable to ipso substitution. Fluorescence spectroscopy and cyclic voltammetry investigations suggest that the interaction between excited acetone and aryl triflate is essential to these couplings. The results in this report are anticipated to provide new opportunities to perform cross-couplings.

Transition-Metal-Free C–C, C–O, and C–N Cross-Couplings Enabled by Light

Primary anilines are essential building blocks to synthesize various pharmaceuticals, agrochemicals, pigments, electronic materials, and others. To date, the syntheses of primary anilines mostly rely on the reduction of nitroarenes or the transition-metal-catalyzed Ullmann, Buchwald–Hartwig and Chan–Lam cross-coupling reactions with ammonia, in which non-renewable petroleum-based chemicals are typically used as feedstocks via multiple step syntheses. A long-standing scientific challenge is to synthesize various primary anilines directly from renewable sources. Herein, we report a general method to directly convert a broad range of phenols into the corresponding primary anilines with the cheap and widely available hydrazine as both amine and hydride sources with simple Pd/C as the catalyst.

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Direct conversion of phenols into primary anilines with hydrazine catalyzed by palladium

Hydrogen atom abstraction (HAT) from C(sp3)–H bonds of naturally abundant alkanes for alkyl radical generation represents a promising yet underexplored strategy in the alkylation reaction designs since involving stoichiometric oxidants, excessive alkane loading, and limited scope are common drawbacks. Here we report a photo-induced and chemical oxidant-free cross-dehydrogenative coupling (CDC) between alkanes and heteroarenes using catalytic chloride and cobalt catalyst. Couplings of strong C(sp3)–H bond-containing substrates and complex heteroarenes, have been achieved with satisfactory yields. This dual catalytic platform features the in situ engendered chlorine radical for alkyl radical generation and exploits the cobaloxime catalyst to enable the hydrogen evolution for catalytic turnover. The practical value of this protocol was demonstrated by the gram-scale synthesis of alkylated heteroarene with merely 3 equiv. alkane loading. Hydrogen atom abstraction from C(sp3)–H bonds of naturally abundant alkanes for alkyl radical generation represents a promising yet underexplored strategy in the alkylation reaction designs. Here the authors show a photo-induced and chemical oxidant-free cross-dehydrogenative coupling between alkanes and heteroarenes using catalytic chloride and cobalt catalyst.

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Jianbin Li

Papers

En Route to Intermolecular Cross-Dehydrogenative Coupling Reactions.

Diacetyl as a “traceless” visible light photosensitizer in metal-free cross-dehydrogenative coupling reactions

Transition-Metal-Free C–C, C–O, and C–N Cross-Couplings Enabled by Light

Direct conversion of phenols into primary anilines with hydrazine catalyzed by palladium

A cross-dehydrogenative C(sp3)-H heteroarylation via photo-induced catalytic chlorine radical generation.