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23 Apr 11:15

[ASAP] Effect of 6,6′-Substituents on Bipyridine-Ligated Ni Catalysts for Cross-Electrophile Coupling

by Haotian Huang, Jose L. Alvarez-Hernandez, Nilay Hazari, Brandon Q. Mercado, and Mycah R. Uehling

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ACS Catalysis
DOI: 10.1021/acscatal.4c00827
23 Apr 11:15

[ASAP] Multimodal Acridine Photocatalysis Enables Direct Access to Thiols from Carboxylic Acids and Elemental Sulfur

by Arka Porey, Seth O. Fremin, Sachchida Nand, Ramon Trevino, William B. Hughes, Shree Krishna Dhakal, Viet D. Nguyen, Samuel G. Greco, Hadi D. Arman, and Oleg V. Larionov

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ACS Catalysis
DOI: 10.1021/acscatal.4c01289
19 Apr 07:16

[ASAP] Photoenzymatic Redox-Neutral Radical Hydrosulfonylation Initiated by FMN

by Linye Jiang, Dannan Zheng, Xiaoyang Chen, Dong Cui, Xinyu Duan, Zhiguo Wang, Jingyan Ge, and Jian Xu

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ACS Catalysis
DOI: 10.1021/acscatal.4c00350
19 Apr 07:12

Dynamics of Coordinated Phosphonate Group Directly Observed by 17O‐NMR in Lanthanide(iii) Complexes of a Mono(ethyl phosphonate) DOTA Analogue

by Adam Svítok, Jan Blahut, Peter Urbanovský, Petr Hermann
Dynamics of Coordinated Phosphonate Group Directly Observed by 17O-NMR in Lanthanide(iii) Complexes of a Mono(ethyl phosphonate) DOTA Analogue

Dynamics of mutual exchange of coordinated and non-coordinated oxygen atoms on phosphate anion analogue was measured for the first time. It proceeds through a sterically demanding four-membered κ2-O2P chelate. Its energy barrier steeply increases for smaller Ln(III) ions and is accessible only in more flexible TSA isomers of large Ln(III) ions.


Abstract

Biological phosphates can coordinate metal ions and their complexes are common in living systems. Dynamics of mutual oxygen atom exchange in the tetrahedral group in complexes has not been investigated. Here, we present a direct experimental proof of exchange (“phosphonate rotation”) in model Ln(III) complexes of monophosphonate H4dota analogue which alters phosphorus atom chirality of coordinated phosphonate monoester. Combination of macrocycle-based isomerism with P-based chirality leads to several diastereoisomers. (Non)-coordinated oxygen atoms were distinguished through 17O-labelled phosphonate group and their mutual exchange was followed by various NMR techniques and DFT calculations. The process is sterically demanding and occurs through bulky bidentate (κ2-PO2)− coordination and was observed only in twisted-square antiprism (TSA) diastereoisomer of large Ln(III) ions. Its energy demands increase for smaller Ln(III) ions (298ΔG ≠(exp./DFT)=51.8/52.1 and 61.0/71.5 kJ mol−1 for La(III) and Eu(III), respectively). These results are helpful in design of such complexes as MRI CA and for protein paramagnetic NMR probes. It demonstrates usefulness of 17O NMR to study solution dynamics in complexes involving phosphorus acid derivatives and it may inspire use of this method to study dynamics of phosphoric acid derivatives (as e. g. phosphorus acid-based inhibitors of metalloenzymes) in different areas of chemistry.

11 Apr 08:07

[ASAP] Editing Tetrasubstituted Carbon: Dual C–O Bond Functionalization of Tertiary Alcohols Enabled by Palladium-Based Dyotropic Rearrangement

by Tristan Delcaillau, Baochao Yang, Qian Wang, and Jieping Zhu

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Journal of the American Chemical Society
DOI: 10.1021/jacs.4c02924
05 Apr 19:35

The Future of Chemical Sciences is Sustainable

by Sharon Mitchell, Antonio J. Martín, Gonzalo Guillén‐Gosálbez, Javier Pérez‐Ramírez
The Future of Chemical Sciences is Sustainable

Chemistry has the potential to drive global sustainability efforts, but how to ensure its optimal impact is not always obvious. Through analysis of green, circular, and sustainable chemistry concepts, this Scientific Perspective identifies unified triple E priorities, covering environmental, economic, and equity pillars, and categorizes associated metrics. Case studies illustrate how these can be used to guide research and decisions.


Abstract

Chemistry, a vital tool for sustainable development, faces a challenge due to the lack of clear guidance on actionable steps, hindering the optimal adoption of sustainability practices across its diverse facets from discovery to implementation. This Scientific Perspective explores established frameworks and principles, proposing a conciliated set of triple E priorities anchored on Environmental, Economic, and Equity pillars for research and decision making. We outline associated metrics, crucial for quantifying impacts, classifying them according to their focus areas and scales tackled. Emphasizing catalysis as a key driver of sustainable synthesis of chemicals and materials, we exemplify how triple E priorities can practically guide the development and implementation of processes from renewables conversions to complex customized products. We summarize by proposing a roadmap for the community aimed at raising awareness, fostering academia–industry collaboration, and stimulating further advances in sustainable chemical technologies across their broad scope.

26 Mar 15:03

A focus on molecular representation learning for the prediction of chemical properties

Chem. Sci., 2024, 15,5052-5055
DOI: 10.1039/D4SC90043J, Commentary
Open Access Open Access
Creative Commons Licence&nbsp This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Yonatan Harnik, Anat Milo
Molecular representation learning (MRL) holds significant potential for predicting diverse chemical properties. In this focus article, we will provide context for applications of MRL in chemistry and the significance of King-Smith's recently published work within this evolving field.
The content of this RSS Feed (c) The Royal Society of Chemistry
26 Mar 15:00

Iodoarene-directed photoredox β-C(sp3)–H arylation of 1-(o-iodoaryl)alkan-1-ones with cyanoarenes via halogen atom transfer and hydrogen atom transfer

Chem. Sci., 2024, 15,6522-6529
DOI: 10.1039/D3SC06637A, Edge Article
Open Access Open Access
Liang Zeng, Chong-Hui Xu, Xiu-Yuan Zou, Qing Sun, Ming Hu, Xuan-Hui Ouyang, De-Liang He, Jin-Heng Li
Radical-mediated direct photoredox β-C(sp3)–H arylation of 1-(o-iodoaryl)alkan-1-ones with cyanoarenes directed by an iodoarene group is depicted.
The content of this RSS Feed (c) The Royal Society of Chemistry
26 Mar 14:35

[ASAP] Electrocatalytic Pathways to the Formation of C–N Bonds

by Dimitra Anastasiadou and Marta Costa Figueiredo

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ACS Catalysis
DOI: 10.1021/acscatal.3c04912
26 Mar 14:32

[ASAP] Ketyl Radical Generation by Photoexcited Palladium and Development of Organopalladium-Type Reactions

by Kosaku Tanaka, III

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ACS Catalysis
DOI: 10.1021/acscatal.4c00510
26 Mar 13:57

Electrochemical Dehydration of Dicarboxylic Acids to Their Cyclic Anhydrides

by Johannes Schneider, Andreas P. Häring, Siegfried R Waldvogel
Electrochemical Dehydration of Dicarboxylic Acids to Their Cyclic Anhydrides

An electrochemical dehydrative reaction of dicarboxylic acids to their cyclic anhydrides is presented. The electrochemically generated anhydrides can be directly employed for amidation reactions. The mechanism of the reaction was investigated by 18O isotope labeling, revealing the formation of sulfate during electrolysis.


Abstract

An intramolecular electrochemical dehydration reaction of dicarboxylic acids to their cyclic anhydrides is presented. This electrolysis allows dicarboxylic acids as naturally abundant, inexpensive, safe, and readily available starting materials to be transformed into carboxylic anhydrides under mild reaction conditions. No conventional dehydration reagent is required. The obtained cyclic anhydrides are highly valuable reagents in organic synthesis, and in this report, we use them in-situ for acylation reactions of amines to synthesize amides. This work is part of the recent progress in electrochemical dehydration, which – in contrast to electrochemical dehydrogenative reactions for example – is an underexplored field of research. The reaction mechanism was investigated by 18O isotope labeling, revealing the formation of sulfate by electrochemical oxidation and hydrolysis of the thiocyanate-supporting electrolyte. This transformation is not a classical Kolbe electrolysis, because it is non-decarboxylative, and all carbon atoms of the carboxylic acid starting material are contained in the carboxylic anhydride. In total, 20 examples are shown with NMR yields up to 71 %.

26 Mar 13:50

[ASAP] Correction to “Mechanisms for the Oxidative Addition of Palladium(0) Complexes to Arenediazonium Salts”

by Henrique Esteves, Vitor H. Menezes da Silva, Carlos R. D. Correia, and Ataualpa A. C. Braga
Organometallics
DOI: 10.1021/acs.organomet.4c00040
13 Mar 10:06

[ASAP] Unlocking the Potential of Oxidative Asymmetric Catalysis with Continuous Flow Electrochemistry

by Peng-Yu Chen, Chong Huang, Liang-Hua Jie, Bin Guo, Shaobin Zhu, and Hai-Chao Xu

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Journal of the American Chemical Society
DOI: 10.1021/jacs.4c00878
13 Mar 10:06

[ASAP] Development of a General Organophosphorus Radical Trap: Deoxyphosphonylation of Alcohols

by Noah B. Bissonnette, Niels Bisballe, Andrew V. Tran, James A. Rossi-Ashton, and David W. C. MacMillan

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Journal of the American Chemical Society
DOI: 10.1021/jacs.4c00557
04 Mar 20:41

[ASAP] Computationally Guided Ligand Discovery from Compound Libraries and Discovery of a New Class of Ligands for Ni-Catalyzed Cross-Electrophile Coupling of Challenging Quinoline Halides

by Sergei Tcyrulnikov, Aran K. Hubbell, Dylan Pedro, Giselle P. Reyes, Sebastien Monfette, Daniel J. Weix, and Eric C. Hansen

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Journal of the American Chemical Society
DOI: 10.1021/jacs.3c14607
27 Feb 19:09

[ASAP] Ni-Catalyzed Photochemial Sulfamidation of Aryl Chlorides with Soluble Organic Amine as Base

by Geyang Song, Jiameng Song, Jianyang Dong, Gang Li, Juan Fan, and Dong Xue

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Organometallics
DOI: 10.1021/acs.organomet.3c00506
27 Feb 12:48

Reactivity of Superbasic Carbanions Generated via Reductive Radical‐Polar Crossover in the Context of Photoredox Catalysis

by Sascha Grotjahn, Christina Graf, Jan Zelenka, Aryaman Pattanaik, Lea Müller, Roger Jan Kutta, Julia Rehbein, Jana Roithová, Ruth M. Gschwind, Patrick Nuernberger, Burkhard König
Reactivity of Superbasic Carbanions Generated via Reductive Radical-Polar Crossover in the Context of Photoredox Catalysis

Photocatalytic reactions with a reductive radical-polar crossover (RRPCO) involve intermediates with carbanionic reactivity. These are best described as free carbanions. Reactions with such carbanions depend on the balance between their nucleophilicity and basicity. Deprotonation of reaction partners and common organic solvents such as acetonitrile, dimethylformamide, and dimethylsulfoxide is the main competing reaction to nucleophilic addition.


Abstract

Photocatalytic reactions involving a reductive radical-polar crossover (RRPCO) generate intermediates with carbanionic reactivity. Many of these proposed intermediates resemble highly reactive organometallic compounds. However, conditions of their formation are generally not tolerated by their isolated organometallic versions and often a different reactivity is observed. Our investigations on their nature and reactivity under commonly used photocatalytic conditions demonstrate that these intermediates are indeed best described as free, superbasic carbanions capable of deprotonating common polar solvents usually assumed to be inert such as acetonitrile, dimethylformamide, and dimethylsulfoxide. Their basicity not only towards solvents but also towards electrophiles, such as aldehydes, ketones, and esters, is comparable to the reactivity of isolated carbanions in the gas-phase. Previously unsuccessful transformations thought to result from a lack of reactivity are explained by their high reactivity towards the solvent and weakly acidic protons of reaction partners. An intuitive explanation for the mode of action of photocatalytically generated carbanions is provided, which enables methods to verify reaction mechanisms proposed to involve an RRPCO step and to identify the reasons for the limitations of current methods.

26 Feb 19:08

[ASAP] Implementing a Doping Approach for Poly(methyl methacrylate) Recycling in a Circular Economy

by Mason T. Chin, Tiangang Yang, Kevin P. Quirion, Christina Lian, Peng Liu, Jie He, and Tianning Diao

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Journal of the American Chemical Society
DOI: 10.1021/jacs.3c13223
26 Feb 19:06

[ASAP] ProPhos: A Ligand for Promoting Nickel-Catalyzed Suzuki-Miyaura Coupling Inspired by Mechanistic Insights into Transmetalation

by Jin Yang, Michelle C. Neary, and Tianning Diao

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Journal of the American Chemical Society
DOI: 10.1021/jacs.4c00370
26 Feb 19:01

Electrochemically Driven para‐Selective C(sp2)−H Alkylation Enabled by Activation of Alkyl Halides without Sacrificial Anodes

by Xinling Li, Weijie Deng, Yating Wen, Ziliang Wang, Jianfeng Zhou, Zhenjie Li, Yibiao Li, Jinhui Hu, Yubing Huang
Electrochemically Driven para-Selective C(sp2)−H Alkylation Enabled by Activation of Alkyl Halides without Sacrificial Anodes

An electrochemically driven para-selective C(sp2)−H alkylation of electron-deficient arenes (aryl esters, aldehydes, nitriles, and ketones) has been achieved with alkyl halides (I, Br, Cl) as a coupling partner. Under mild electrolytic conditions, a variety of alkylated arenes are obtained in one step through the formation of C(sp2)-C(sp3) bonds. Notably, the reaction enables the activation of alkyl halides in the absence of sacrificial anodes.


Abstract

With alkyl halides (I, Br, Cl) as a coupling partner, an electrochemically driven strategy for para-selective C(sp2)−H alkylation of electron-deficient arenes (aryl esters, aldehydes, nitriles, and ketones) has been achieved to access diverse alkylated arenes in one step. The reaction enables the activation of alkyl halides in the absence of sacrificial anodes, achieving the formation of C(sp2)-C(sp3) bonds under mild electrolytic conditions. The utility of this protocol is reflected in high site selectivity, broad substrate scope, and scalable.

26 Feb 18:59

[ASAP] Synergistic Dual Catalysis in Stereodivergent Synthesis

by Liang Wei, Cong Fu, Zuo-Fei Wang, Hai-Yan Tao, and Chun-Jiang Wang

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ACS Catalysis
DOI: 10.1021/acscatal.3c06267
21 Feb 19:24

s-Block metal complexes of superbulky (tBu3Si)2N−: a new weakly coordinating anion?

Chem. Sci., 2024, 15,4386-4395
DOI: 10.1039/D3SC06896J, Edge Article
Open Access Open Access
Creative Commons Licence&nbsp This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Christian Knüpfer, Lukas Klerner, Jonathan Mai, Jens Langer, Sjoerd Harder
The extremely challenging deprotonation of the amine (tBu3Si)2NH led to a range of s-block metal complexes with superbulky (tBu3Si)2N−. Depending on metal and solvent, (tBu3Si)2N− can be classified as a halogen-free weakly coordinating anion.
The content of this RSS Feed (c) The Royal Society of Chemistry
17 Feb 08:29

[ASAP] Enantiocovergent Cross-Coupling Reaction with 1,4-Dihydropyridine Derivatives via Photoinduced Nickel Catalysis

by Tongtong Li, Lifeng Luo, Xiaokai Cheng, and Zhan Lu

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ACS Catalysis
DOI: 10.1021/acscatal.3c05521
12 Feb 13:56

Alkene Thianthrenation Unlocks Diverse Cation Synthons: Recent Progress and New Opportunities

by Min Kim, Karina Targos, Dylan E. Holst, Diana J. Wang, Zachary K. Wickens
Alkene Thianthrenation Unlocks Diverse Cation Synthons: Recent Progress and New Opportunities

The transformation of alkenes into thianthrene-derived cationic electrophiles unlocks a suite of net oxidative alkene transformations that have been elusive using conventional strategies. These linchpin intermediates can be generated selectively and undergo a diverse array of mechanistically distinct reactions with abundant nucleophiles.


Abstract

Oxidative alkene functionalization reactions are a fundamental class of complexity-building organic transformations. However, the majority of established approaches rely on electrophilic reagents that limit the diversity of groups that can be installed. Recent advances have established a new approach that instead relies on the transformation of alkenes into thianthrene-derived cationic electrophiles. These linchpin intermediates can be generated selectively and undergo a diverse array of mechanistically distinct reactions with abundant nucleophiles. Taken together, this unlocks a suite of net oxidative alkene transformations that have been elusive using conventional strategies. This Minireview describes these advances and is organized around the three distinct synthons formally accessible from alkenes via thianthrenation: 1) alkenyl cations; 2) vicinal dications; 3) allyl cations. Throughout the Minireview, we illustrate how thianthrenium salts address key limitations endemic to classic alkene-derived electrophiles and highlight the mechanistic origins of these distinctions wherever possible.

07 Feb 11:01

[ASAP] DFT-Enabled Development of Hemilabile (P∧N) Ligands for Gold(I/III) RedOx Catalysis: Application to the Thiotosylation of Aryl Iodides

by Karim Muratov, Emil Zaripov, Maxim V. Berezovski, and Fabien Gagosz

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Journal of the American Chemical Society
DOI: 10.1021/jacs.3c08943
05 Feb 08:07

[ASAP] Flavin-Mediated Photocatalysis Provides a General Platform for Sulfide C–H Functionalization

by Alex S. Anderton, Oliver J. Knowles, James A. Rossi-Ashton, and David J. Procter

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ACS Catalysis
DOI: 10.1021/acscatal.3c05785
05 Feb 08:06

[ASAP] Recent Advances in Theoretical Studies on Cu-Mediated Bond Formation Mechanisms Involving Radicals

by Ji-Ren Liu, Guo-Xiong Xu, Li-Gao Liu, Shuo-Qing Zhang, and Xin Hong

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ACS Catalysis
DOI: 10.1021/acscatal.3c06042
05 Feb 08:03

Electrochemical Ni‐Catalyzed Decarboxylative C(sp3)−N Cross‐Electrophile Coupling

by Yue-Ming Cai, Xiao-Ting Liu, Lin-Lin Xu, ming shang
Electrochemical Ni-Catalyzed Decarboxylative C(sp3)−N Cross-Electrophile Coupling

Ni-catalyzed decarboxylative C(sp3)−N cross-coupling of redox active ester and oxime esters was realized through electrochemical cathodic reduction. Mechanistic studies unveil a high-valent nickel species-driven reductive elimination pathway, rather than direct radical-radical coupling. The utility of this methodology was demonstrated through a broad scope (1°, 2°, 3° carboxylic acids) and late-stage functionalization of complex molecules.


Abstract

A new electrochemical transformation is presented that enables chemists to couple simple alkyl carboxylic acid derivatives with an electrophilic amine reagent to construct C(sp3)−N bond. The success of this reaction hinges on the merging of cooperative electrochemical reduction with nickel catalysis. The chemistry exhibits a high degree of practicality, showcasing its wide applicability with 1°, 2°, 3° carboxylic acids and remarkable compatibility with diverse functional groups, even in the realm of late-stage functionalization. Furthermore, extensive mechanistic studies have unveiled the engagement of alkyl radicals and iminyl radicals; and elucidated the multifaceted roles played by i Pr2O, Ni catalyst, and electricity.

26 Jan 10:02

[ASAP] Photochemical Organocatalytic Synthesis of Thioethers from Aryl Chlorides and Alcohols

by Shuo Wu, Thomas Hin-Fung Wong, Paolo Righi, and Paolo Melchiorre

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Journal of the American Chemical Society
DOI: 10.1021/jacs.3c13900
26 Jan 10:01

[ASAP] Dicationic Acridinium/Carbene Hybrids as Strongly Oxidizing Photocatalysts

by Samaresh C. Sau, Matthias Schmitz, Chris Burdenski, Marcel Baumert, Patrick W. Antoni, Christoph Kerzig, and Max M. Hansmann

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Journal of the American Chemical Society
DOI: 10.1021/jacs.3c12766