Photo-induced carboxylation of C(sp)-S bonds in aryl thiols and derivatives with CO.

Aryl thiols have proven to be a useful class of electron donors and hydrogen atom sources in photochemical processes. However, the direct activation and functionalization of C(sp)-S bonds in aryl thiols remains elusive in the field of photochemistry. Herein, a photochemical carboxylation of C(sp)-S bonds in aryl thiols with CO is reported, providing a synthetic route to important aryl carboxylic acids.

Nickel-Catalyzed Atroposelective Carbo-Carboxylation of Alkynes with CO: En Route to Axially Chiral Carboxylic Acids.

Precise synthesis of carboxylic acids via catalytic carboxylation with CO is highly appealing. Although considerable advancements have been achieved in difunctionalizing carboxylation of unsaturated hydrocarbons, the asymmetric variants are conspicuously underdeveloped, particularly in addressing axially chiral alkenes. Herein, we report the first catalytic atroposelective carboxylation of alkynes with CO.

Recent Advances in Electrochemical Carboxylation with CO.

ConspectusCarbon dioxide (CO) is recognized as a greenhouse gas and a common waste product. Simultaneously, it serves as an advantageous and commercially available C1 building block to generate valuable chemicals. Particularly, carboxylation with CO is considered a significant method for the direct and sustainable production of important carboxylic acids.

Silencing LINC00987 ameliorates adriamycin resistance of acute myeloid leukemia via miR-4458/HMGA2 axis.

Background: Most patients with acute myeloid leukemia (AML) eventually develop drug resistance, leading to a poor prognosis. Dysregulated long gene non coding RNAs (lincRNAs) have been implicated in chemoresistance in AML. Unfortunately, the effects of lincRNAs which participate in regulating the Adriamycin (ADR) resistance in AML cells remain unclear.

Atropisomeric Carboxylic Acids Synthesis via Nickel-Catalyzed Enantioconvergent Carboxylation of Aza-Biaryl Triflates with CO.

Upgrading CO to value-added chiral molecules via catalytic asymmetric C-C bond formation is a highly important yet challenging task. Although great progress on the formation of centrally chiral carboxylic acids has been achieved, catalytic construction of axially chiral carboxylic acids with CO has never been reported to date. Herein, we report the first catalytic asymmetric synthesis of axially chiral carboxylic acids with CO, which is enabled by nickel-catalyzed dynamic kinetic asymmetric reductive carboxylation of racemic aza-biaryl triflates.

Cu-Catalyzed Asymmetric Dicarboxylation of 1,3-Dienes with CO.

Dicarboxylic acids and derivatives are important building blocks in organic synthesis, biochemistry, and the polymer industry. Although catalytic dicarboxylation with CO represents a straightforward and sustainable route to dicarboxylic acids, it is still highly challenging and limited to generation of achiral or racemic dicarboxylic acids. To date, catalytic asymmetric dicarboxylation with CO to give chiral dicarboxylic acids has not been reported.

Arylcarboxylation of unactivated alkenes with CO via visible-light photoredox catalysis.

Photocatalytic carboxylation of alkenes with CO is a promising and sustainable strategy to synthesize high value-added carboxylic acids. However, it is challenging and rarely investigated for unactivated alkenes due to their low reactivities. Herein, we report a visible-light photoredox-catalyzed arylcarboxylation of unactivated alkenes with CO, delivering a variety of tetrahydronaphthalen-1-ylacetic acids, indan-1-ylacetic acids, indolin-3-ylacetic acids, chroman-4-ylacetic acids and thiochroman-4-ylacetic acids in moderate-to-good yields.

Electroreductive Dicarboxylation of Unactivated Skipped Dienes with CO.

Carboxylation of easily available alkenes with CO is highly important to afford value-added carboxylic acids. Although dicarboxylation of activated alkenes, especially 1,3-dienes, has been widely investigated, the challenging dicarboxylation of unactivated 1,n-dienes (n>3) with CO remains unexplored. Herein, we report the first dicarboxylation of unactivated skipped dienes with CO via electrochemistry, affording valuable dicarboxylic acids.

Photocatalytic Carboxylation of C-N Bonds in Cyclic Amines with CO by Consecutive Visible-Light-Induced Electron Transfer.

Visible-light photocatalytic carboxylation with CO is highly important. However, it still remains challenging for reluctant substrates with low reduction potentials. Herein, we report a novel photocatalytic carboxylation of C-N bonds in cyclic amines with CO via consecutive photo-induced electron transfer (ConPET).

Electrochemical reactor dictates site selectivity in N-heteroarene carboxylations.

Pyridines and related N-heteroarenes are commonly found in pharmaceuticals, agrochemicals and other biologically active compounds. Site-selective C-H functionalization would provide a direct way of making these medicinally active products. For example, nicotinic acid derivatives could be made by C-H carboxylation, but this remains an elusive transformation.

Electrochemical Ring-Opening Dicarboxylation of Strained Carbon-Carbon Single Bonds with CO: Facile Synthesis of Diacids and Derivatization into Polyesters.

Diacids are important monomers in the polymer industry to construct valuable materials. Dicarboxylation of unsaturated bonds, such as alkenes and alkynes, with CO has been demonstrated as a promising synthetic method. However, dicarboxylation of C─C single bonds with CO has rarely been investigated.

Nickel-catalyzed electrochemical carboxylation of unactivated aryl and alkyl halides with CO.

Electrochemical catalytic reductive cross couplings are powerful and sustainable methods to construct C-C bonds by using electron as the clean reductant. However, activated substrates are used in most cases. Herein, we report a general and practical electro-reductive Ni-catalytic system, realizing the electrocatalytic carboxylation of unactivated aryl chlorides and alkyl bromides with CO.

Visible-light photoredox-catalyzed umpolung carboxylation of carbonyl compounds with CO.

Photoredox-mediated umpolung strategy provides an alternative pattern for functionalization of carbonyl compounds. However, general approaches towards carboxylation of carbonyl compounds with CO remain scarce. Herein, we report a strategy for visible-light photoredox-catalyzed umpolung carboxylation of diverse carbonyl compounds with CO by using Lewis acidic chlorosilanes as activating/protecting groups.

Radical Carboxylative Cyclizations and Carboxylations with CO.

Carbon dioxide (CO) is not only a greenhouse gas and a common waste product but also an inexpensive, readily available, and renewable carbon resource. It is an important one-carbon (C1) building block in organic synthesis for the construction of valuable compounds. However, its utilization is challenging owing to its thermodynamic stability and kinetic inertness.

α-Amino Acids and Peptides as Bifunctional Reagents: Carbocarboxylation of Activated Alkenes via Recycling CO.

Carboxylic acids, including amino acids (AAs), have been widely used as reagents for decarboxylative couplings. In contrast to previous decarboxylative couplings that release CO as a waste byproduct, herein we report a novel strategy with simultaneous utilization of both the alkyl and carboxyl components from carboxylic acids. Under this unique strategy, carboxylic acids act as bifunctional reagents in the redox-neutral carbocarboxylation of alkenes.

Visible-Light Photoredox-Catalyzed Ring-Opening Carboxylation of Cyclic Oxime Esters with CO.

The carboxylation of cyclic oxime esters with carbon dioxide via visible-light photoredox catalysis is demonstrated for the first time. A variety of cyclic oxime esters undergo ring-opening C-C bond cleavage and carboxylation to give cyanoalkyl-containing carboxylic acids in moderate to good yields. Moreover, this methodology features mild reaction conditions (room temperature, 1 atm), wide substrate scope, good functional group tolerance as well as facile derivations of products.

Reductive dearomative arylcarboxylation of indoles with CO via visible-light photoredox catalysis.

Catalytic reductive coupling of two electrophiles and one unsaturated bond represents an economic and efficient way to construct complex skeletons, which is dominated by transition-metal catalysis via two electron transfer. Herein, we report a strategy of visible-light photoredox-catalyzed successive single electron transfer, realizing dearomative arylcarboxylation of indoles with CO. This strategy avoids common side reactions in transition-metal catalysis, including ipso-carboxylation of aryl halides and β-hydride elimination.

A VIT-like transporter facilitates iron transport into nodule symbiosomes for nitrogen fixation in soybean.

Effective legume-rhizobia symbiosis depends on efficient nutrient exchange. Rhizobia need to synthesize iron-containing proteins for symbiotic nitrogen fixation (SNF) in nodules, which depends on host plant-mediated iron uptake into the symbiosome. We functionally investigated a pair of vacuolar iron transporter like (VTL) genes, GmVTL1a/b, in soybean (Glycine max) and evaluated their contributions to SNF, including investigations of gene expression patterns, subcellular localization, and mutant phenotypes.

Transition metal-free phosphonocarboxylation of alkenes with carbon dioxide via visible-light photoredox catalysis.

Catalytic difunctionalization of alkenes has been an ideal strategy to generate structurally complex molecules with diverse substitution patterns. Although both phosphonyl and carboxyl groups are valuable functional groups, the simultaneous incorporation of them via catalytic difunctionalization of alkenes, ideally from abundant, inexpensive and easy-to-handle raw materials, has not been realized. Herein, we report the phosphonocarboxylation of alkenes with CO via visible-light photoredox catalysis.

Magnesium Deficiency Triggers SGR-Mediated Chlorophyll Degradation for Magnesium Remobilization.

Magnesium (Mg) is a relatively mobile element that is remobilized in plants under Mg-limited conditions through transport from old to young tissues. However, the physiological and molecular mechanisms underlying Mg remobilization in plants remain poorly understood. In this study, we investigated Mg remobilization in rice () as facilitated through a Mg dechelatase gene involved in chlorophyll degradation, - ().

Visible-Light-Driven External-Reductant-Free Cross-Electrophile Couplings of Tetraalkyl Ammonium Salts.

Cross-electrophile couplings between two electrophiles are powerful and economic methods to generate C-C bonds in the presence of stoichiometric external reductants. Herein, we report a novel strategy to realize the first external-reductant-free cross-electrophile coupling via visible-light photoredox catalysis. A variety of tetraalkyl ammonium salts, bearing primary, secondary, and tertiary C-N bonds, undergo selective couplings with aldehydes/ketone and CO.

Selective and Catalytic Hydrocarboxylation of Enamides and Imines with CO to Generate α,α-Disubstituted α-Amino Acids.

The first catalytic hydrocarboxylation of enamides and imines with CO to generate valuable α,α-disubstituted α-amino acids is reported. Notably, excellent chemo- and regio-selectivity are achieved, significantly different from previous reports on β-carboxylation of enamides, homocoupling or reduction of imines. Moreover, this transition-metal-free procedure exhibits low loading of an inexpensive catalyst, easily available substrates, mild reaction conditions, high efficiency, facile scalability and easy product derivatization, providing great potential for application in organic synthesis, pharmaceutical chemistry, and biochemistry.

Synthesis of tetronic acids from propargylic alcohols and CO.

A direct and practical synthesis of important tetronic acids from easily available propargylic alcohols and carbon dioxide is reported for the first time. This transition-metal-free transformation features high atom- and step-economy, mild reaction conditions, good functional group tolerance and high yield. Preliminary mechanistic studies suggest that the reaction proceeds via cyclization to give alkylidene cyclic carbonate, ring-opening and re-cyclization processes.

Highly Regio- and Enantioselective Copper-Catalyzed Reductive Hydroxymethylation of Styrenes and 1,3-Dienes with CO.

Herein, we report a highly regio- and enantioselective copper-catalyzed reductive hydroxymethylation of styrenes and 1,3-dienes with 1 atm of CO. Diverse important chiral homobenzylic alcohols were readily prepared from styrenes. Moreover, a variety of 1,3-dienes also were converted to chiral homoallylic alcohols with high yields and excellent regio-, enantio-, and Z/E-selectivities.

Visible-Light-Driven Palladium-Catalyzed Radical Alkylation of C-H Bonds with Unactivated Alkyl Bromides.

Reported herein is a novel visible-light photoredox system with Pd(PPh ) as the sole catalyst for the realization of the first direct cross-coupling of C(sp )-H bonds in N-aryl tetrahydroisoquinolines with unactivated alkyl bromides. Moreover, intra- and intermolecular alkylations of heteroarenes were also developed under mild reaction conditions. A variety of tertiary, secondary, and primary alkyl bromides undergo reaction to generate C(sp )-C(sp ) and C(sp )-C(sp ) bonds in moderate to excellent yields.