LG

Shared posts

22 Feb 15:06

[ASAP] Revealing the Mechanism of TEMPO-Hypervalent Iodine(III) Oxidation of Alcohols

by Michael Bingham, Tapas R. Pradhan, Dhananjay Bhattacherjee, Rawiyah Alkahtani, Paul Kavanagh, Thomas Wirth, and Paul Dingwall

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.5c21609
22 Feb 15:04

[ASAP] Transition-Metal Catalyzed Carbene Transformations via Ring Strain-Release Processes

by Fukuan Zhang, Hui Wen, and Yaojia Jiang

TOC Graphic

ACS Catalysis
DOI: 10.1021/acscatal.5c09031
22 Feb 15:03

[ASAP] Automated DFT-Machine Learning Integration Enables Data-Efficient and Generalizable Feasibility Predictions in Metallaphotoredox sp2–sp3 Cross-Coupling Reactions

by Michele Assante, Sara Pahlen, Brenda Pijper, Lili Cao, Ole Specht, Nadja Simeth, Alexei Lapkin, Clive Green, Ola Engkvist, Giulia Bergonzini, and Mikhail Kabeshov

TOC Graphic

ACS Catalysis
DOI: 10.1021/acscatal.5c07857
22 Feb 15:01

[ASAP] DFT-Based Multiscale Modeling of Heterogeneous (Electro)Catalytic Reactions

by Minttu M. Smith, Laureline Treps, Marko M. Melander, Vesa Apaja, and Karoliina Honkala

TOC Graphic

ACS Catalysis
DOI: 10.1021/acscatal.5c07967
22 Feb 14:59

Machine Learning‐Guided Design of a Flexible Highly Conductive Additive‐Free Polymer Cathode

by Yan Zhang, Xuelian Liu, Yichen Wei, Weiran Wang, Lu Bai, Alexandru Vlad, Junzhong Wang, Jiande Wang
Machine Learning-Guided Design of a Flexible Highly Conductive Additive-Free Polymer Cathode

We present the first flexible, binder- and carbon-free organic cathode (poly-benzodifurandione, PBFO) for Li/Na-ion batteries, discovered via ML screening of the ZINC database. The flexible PBFO film exhibits a breakthrough conductivity of 5.9×102 S cm−1—the highest among additive-free organic cathodes—and delivers a reversible capacity of 262 mAh g−1 with an average voltage of 2.5 V versus Li+/Li and good stability.


ABSTRACT

Organic cathode materials (OCMs) are promising sustainable alternatives to inorganic counterparts for next-generation batteries, yet their widespread application is largely hindered by intrinsically low electrical conductivity (below 10−6 S cm−1) and material dissolution. The vast chemical space for exploration complicates the discovery of optimal OCMs. In this work, we utilized a machine learning (ML)-based discovery process with a pretrained transformer model in ZINC organic molecules database, yielding a couple of potential high-performance OCMs candidates, including isoindigo-type redox units. The output of such efficient screening inspires the design of poly-benzodifurandione (PBFO) as a free-standing cathode material for high-performance Li-ion and Na-ion storage. The flexible PBFO film exhibits a breakthrough conductivity of 5.9×102 S cm−1, setting a new benchmark for additive-free organic cathodes. The neat PBFO cathodes achieve a reversible capacity of 262 mAh g−1 averaging at 2.5 V versus Li+/Li at 25 mA g−1, delivering a high electrode-level energy density of 655 Wh kg−1, among the highest reported for OCMs. This work provides the first flexible, high-conductivity organic cathodes without conductive additives and binders, opening a new direction toward viable organic batteries.

22 Feb 14:54

Anomeric Amides: Valuable Reagents in Synthetic Organic Chemistry

by Arushi Garg, Jordan Vigier, Hélène Lebel, Tatiana Besset
Anomeric Amides: Valuable Reagents in Synthetic Organic Chemistry

Enabling late-stage transformations and skeletal editing, anomeric amides have recently emerged as powerful synthetic tools. Due to their unique properties, anomeric amides have been employed in reactions ranging from amination to halogenation. This minireview provides an overview of recent progress in using anomeric amides across a variety of synthetic transformations.


ABSTRACT

The quest for synthetic tools to achieve molecular complexity is of paramount importance. In recent years, strategies have been developed for the late-stage functionalization of molecules. Anomeric amides have emerged as valuable reagents in this active research area due to their broad range of synthetic applications, and they continue to draw growing interest from the scientific community. This minireview aims to discuss and highlight recent progress in using anomeric amides across a variety of synthetic transformations.

22 Feb 14:52

Traces of Elements in the Electrochemical Reductive Amination of Acetone: Uncovering Bi as Substitute for Pb

by Justus Kümper, Yani Guan, Simran Kumari, Sonja D. Mürtz, Philippe Sautet, Regina Palkovits
Traces of Elements in the Electrochemical Reductive Amination of Acetone: Uncovering Bi as Substitute for Pb

This study investigates the impact of various p-block element impurities in the electrochemical reductive amination and reveals with Bi a less toxic alternative for Pb. The utilization of Bi as additive was further optimized by studying the impact of additive concentration, reaction temperature, and cathode material on amine yield, offering new possibilities to synthesize pharmaceuticals sustainably.


ABSTRACT

Amines are broadly utilized as solvents, pharmaceuticals, herbicides, or materials. A benign synthesis route to produce amines from carbonylic substrates is the electrochemical reductive amination, whereby electrons combined with a green proton source like water serve as formal reducing agent. Surprisingly, investigating various p-block elements as mediator for the electrochemical conversion of acetone in presence of methylamine revealed that only elements of the sixth period show an activity. Building up on these findings and the general low toxicity of Bi compared to Tl or Pb, the electrochemical hydrogenation of N-methylpropan-2-imine was optimized by studying the effect of Bi concentration, reaction temperature, and cathode material. Thus, this work highlights Bi as innovative mediator for the electrochemical reductive amination, whereby in presence of a few ppm-amounts of Bi at ambient temperatures high amine yields are achievable.

22 Feb 14:49

The Diarylprolinol Silyl Ethers: After 20 Years Still Opening New Doors in Asymmetric Catalysis

by Enrico Marcantonio, René Slot Bitsch, Karl Anker Jørgensen
The Diarylprolinol Silyl Ethers: After 20 Years Still Opening New Doors in Asymmetric Catalysis

Catalysis Rules! The year 2025 marks the 20th anniversary of diarylprolinol silyl ethers in asymmetric organocatalysis. During the first decade after their discovery, these catalysts have been established as one of the most versatile tools in aminocatalysis. Although now considered mature, recent years have witnessed renewed innovation. We outlined these developments, demonstrating that this remains a rapidly evolving field.


ABSTRACT

A new chapter starts now. Since its discovery in 2005, the diarylprolinol silyl ether catalytic concept has emerged as a general and reliable aminocatalytic tool for the synthesis of enantioenriched molecules. Recently its combination with emerging technologies, as well as its application in more complex molecular systems has opened new avenues for novel enantioenriched scaffolds. In this review, we will highlight these recent developments, unfolding five primary categories that define new horizons in the use of diarylprolinol silyl ethers: Photochemical-, electrochemical-, dual-catalytic transformations, higher-order cycloadditions and applications in total synthesis of complex natural products.

22 Feb 14:47

Staged Diversity‐Constrained Machine Learning for High‐Dimensional Reaction Condition Optimization

by Shu‐Wen Li, Shan Chen, João C. A. Oliveira, Shuo‐Qing Zhang, Lutz Ackermann, Xin Hong
Staged Diversity-Constrained Machine Learning for High-Dimensional Reaction Condition Optimization

Staged diversity-constrained modeling enables efficient navigation of high-dimensional reaction spaces, validated on cross-coupling HTE data and applied to ruthenium-catalyzed meta-C─H functionalization.


ABSTRACT

Optimizing reaction conditions in high-dimensional chemical spaces remains a central challenge in modern synthesis. In this context, we developed and evaluated a staged diversity-constrained machine learning framework that efficiently balances exploration and exploitation during condition optimization. At each stage, a within-batch diversity constraint promotes broad chemical coverage, while the constraint is progressively relaxed to focus on promising subspaces. Systematic evaluation across large-scale palladium-catalyzed C─C and C─N coupling datasets revealed that the number of stages, rather than the exploration portion, was the dominant factor governing optimization efficiency. A comparison with Bayesian optimization (BO) methods shows a dimension-dependent performance trend. Here, the staged diversity-constrained strategy was shown to be more advantageous in higher-dimensional reaction spaces, whereas BO performed better in lower-dimensional settings. Moreover, we developed a user-friendly software tool making the herein developed framework readily accessible for experimental chemists. Our strategy was further applied to challenging ruthenium-catalyzed meta-C─H functionalization involving 11,880 possible conditions, only 44 experiments were required to identify the optimal setup (91% yield). This work provides a validated and practical framework for accelerating high-dimensional reaction condition optimization, bridging data-driven modeling with experimental synthesis.

22 Feb 14:43

Photoinduced Generation of (Boryl)Silyl and (Chloro)Silyl Radicals: Access to Trisubstituted Silylboranes and Chlorosilanes

by Mone Suzuki, Yuki Nagashima
Photoinduced Generation of (Boryl)Silyl and (Chloro)Silyl Radicals: Access to Trisubstituted Silylboranes and Chlorosilanes

A versatile photoinduced hydro(boryl)silylation and hydro(chloro)silylation of alkenes to construct trisubstituted silylboranes and chlorosilanes was achieved through in situ generation of (boryl)silyl radicals or (chloro)silyl radicals. This mild methodology affords high chemoselectivity and broad functional group tolerance to enable direct access to highly complex tetrasubstituted organosilicons and oligosilanes.


ABSTRACT

Trisubstituted silylboranes and chlorosilanes are in high demand for the precise synthesis of tetrasubstituted organosilicons. However, conventional synthetic methods often require harsh conditions and exhibit low functional-group tolerance, limiting their chemical diversity. In this study, we present a versatile photoinduced hydro(boryl)silylation and hydro(chloro)silylation of alkenes to construct trisubstituted silylboranes and chlorosilanes. This method employs the in situ generation of novel silyl radicals, such as (boryl)silyl radicals (R2(pinB)Si•) or (chloro)silyl radicals (R2ClSi•), from hydroborylsilanes or hydrochlorosilanes through highly selective hydrogen-atom transfer. The unprecedented silylboranes and chlorosilanes obtained using this method enable the direct synthesis of highly complex tetrasubstituted organosilicons. Mechanistic studies reveal a photoactivation pathway in which a sulfur radical generated from a combination of ( t BuO)2 and i Pr3SiSH directly facilitates Si─H bond cleavage without inducing any redox events at the Si─B/Si─Cl bonds, enabling radical hydrosilylation with a broad scope of alkenes.

22 Feb 14:42

Benefits of Categorizing Noncovalent Bonds Based on Hydrogen, Halogen, Chalcogen, and Pnictogen Bonds

by Andrea Pizzi, Giancarlo Terraneo, Cristina Lo Iacono, Roberta Beccaria, Arun Dhaka, Giuseppe Resnati
Benefits of Categorizing Noncovalent Bonds Based on Hydrogen, Halogen, Chalcogen, and Pnictogen Bonds

A terminology for electrophile-nucleophile interactions based on names that refer to the electrophile group/atom may offer the advantage to be descriptive, consistent, complete, systematic, clear, and, most important, invariant. Likely, a terminology that employs only the terms σ-hole bond, π-hole bond, and p-hole bond may not.


ABSTRACT

Recent IUPAC recommendations define the halogen bond, the chalcogen bond, and the pnictogen bond as the interactions between nucleophilic sites and electrophilic elements of groups 17, 16, and 15 of the periodic table. In a recent paper Robin Taylor states that, the use of these three terms should be “deprecated” and he raises concern about the proposal that we made in a scientific perspective on this journal to use these three terms, along with the hydrogen bond one, as the core of a taxonomy of chemical interactions, wherein names refer to the electrophile group/atom. Here, we show how Taylor's position conflicts not only with the authoritative position of IUPAC, but also with the common practices of the chemists’ community. Our proposed naming scheme which refers to the electrophile group/atom far from concealing key information, as assumed by Taylor, enables for a precise language whose terminological richness is instrumental in communication efficiency. Our naming scheme presents the advantage to be invariant with respect to the evolving understanding of the nature of chemical interactions and to be tailored to automated database mining, ontology construction, and AI-driven structure–property prediction.

22 Feb 14:38

Hybrid Computational Strategy for Predicting Complex Ligand–Metal Architectures

by Galymzhan Moldagulov, Kisung Lee, Sanzhar Nurgaliyev, Assanali Salem, Anatolii Kuznietsov, Bartosz A. Grzybowski
Hybrid Computational Strategy for Predicting Complex Ligand–Metal Architectures

An accurate “hybrid” model—combining elements of knowledge-based and Machine Learning approaches—is designed to predict metal-ligand coordination modes in a metal-aware fashion and for structurally complex ligands, including hemilabile and haptic ones as well as those with denticity > 6. The model uses coordination rules derived from the X-ray structures derived from the Cambridge Structural Database, applies these rules to create candidate structures, and ranks these candidates using a neural-network-based scoring function.


ABSTRACT

Understanding how metals coordinate to organic ligands is a precondition for the rational design of metal complexes and catalysts. Whereas certain types of ligands are capable of just one easy-to-predict coordination modality, others may present tens and sometimes even hundreds of coordination options (mono-, bi-, or polydentate), and predicting the correct one may be a challenge even to seasoned chemists. The current paper describes a “hybrid” computational approach in which a Machine Learning, ML, algorithm learns to predict complex coordination patterns using knowledge-based “rules” derived from the Cambridge Structural Database, CSD. This model is applicable to a broad scope of ligands (including hemilabile and haptic ones as well as those with denticity > 6) and different metals at different oxidation states. The algorithm's code is disclosed and can be readily deployed in RDKit via our RDMetallics python-wrapper. It is also deployed as a publicly accessible web portal for demonstration and use.

22 Feb 14:36

[ASAP] Ni(DQ)2: A Useful Gateway to Zero-Valent Nickel Complexes

by Wen-Ji He, Shili Fang, Shenghua Yang, Nana Kim, Zhipeng Lu, Camille Z. Rubel, Jake Bailey, Milan Gembicky, Song Lin, Steven R. Wisniewski, and Keary M. Engle

TOC Graphic

Organometallics
DOI: 10.1021/acs.organomet.5c00450
22 Feb 14:36

[ASAP] Selectivity for Exhaustive Cross-Coupling of Dihaloarenes Is Affected by the Interplay between the Halide Byproduct, Solvent, and Ligand

by Nathaniel G. Larson, Matthew P. Sandin, and Sharon R. Neufeldt

TOC Graphic

Organometallics
DOI: 10.1021/acs.organomet.5c00423
22 Feb 14:34

Deoxygenative phosphonation of ketones by titanium

Chem. Sci., 2026, 17,7236-7243
DOI: 10.1039/D5SC09520D, Edge Article
Open Access Open Access
Yuquan Wang, Kai Yin, Xiaobo Pang, Xing-Zhong Shu
Tertiary phosphine oxides are ubiquitous motifs with essential roles across synthetic chemistry and life sciences, yet C(sp3)–P coupling remains underdeveloped.
The content of this RSS Feed (c) The Royal Society of Chemistry
20 Feb 14:47

eCyclopropanation – a safe and scalable electrochemical route to cyclopropanes

Chem. Sci., 2026, 17,7135-7145
DOI: 10.1039/D5SC08940A, Edge Article
Open Access Open Access
Creative Commons Licence&nbsp This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Jamie M. Walsh, Marco Galzignato, Shusuke Hattori, Marylise Triacca, Kevin Lam
Electrochemical generation of diazo compounds from tert-butyl hydrazones enables synchronised Rh-catalysed carbene transfer without diazo accumulation. This inventory-free strategy improves safety and allows gram-scale cyclopropanation in batch and flow.
The content of this RSS Feed (c) The Royal Society of Chemistry
20 Feb 14:45

Simplest mechanism builder algorithm (simba): an automated microkinetic model discovery tool

Chem. Sci., 2026, 17,7533-7550
DOI: 10.1039/D5SC01473E, Edge Article
Open Access Open Access
Creative Commons Licence&nbsp This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
M. Á. de Carvalho Servia, K. K. (M. ) Hii, K. Hellgardt, D. Zhang, E. A. del Rio Chanona
SiMBA automates microkinetic model discovery: it enumerates candidate mechanisms, fits ODE rate laws to data, and selects the simplest accurate pathway via information criteria.
The content of this RSS Feed (c) The Royal Society of Chemistry
19 Feb 15:23

[ASAP] Direct and Enantioselective Acylation of Diverse C(sp3)–H Bonds with Aldehydes

by Zhijun Zhou, Fen Hu, Xinjing Lin, Yuanyuan Ping, and Wangqing Kong

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.5c18382
19 Feb 15:22

[ASAP] Controlled Polymerization Catalysis for the Synthesis of Degradable Amphiphilic Polycarbonates from CO2

by Diego A. Resendiz-Lara, Thomas Habets, Steven P. Armes, and Charlotte K. Williams

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.5c20433
19 Feb 10:32

[ASAP] Photoswitching Lewis Acid Catalysis with Highly Fatigue Resistant Photochromic Boronates

by Lennart Stoess, Jeremy A. Davis, and Lutz Greb

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.5c22962
19 Feb 10:15

[ASAP] Electrochemically Mediated Depolymerization of Polymers Synthesized by Atom Transfer Radical Polymerization

by Victoria Lohmann, Lok Nga Poon, Richard Whitfield, Krzysztof Matyjaszewski, Victor Mougel, and Athina Anastasaki

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.5c20629
19 Feb 10:11

[ASAP] Potassium Bisulfite’s Role in Developing a Robust Platform for Enantioenriched N-Alkylpyridinium Salts as Piperidine Precursors

by Jake D. Selingo, Jacob R. King, Barbara Pio, Andrew J. Neel, Yu-Hong Lam, Robert S. Paton, Matthew L. Maddess, and Andrew McNally

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.5c20464
19 Feb 10:08

[ASAP] Triplet Energy Transfer as a Handle to Tune 1,2-Dialkyldiazene Fragmentation in Radical C(sp3)–C(sp2) Cross-Coupling

by Joffrey Scriven, Deepta Chattapadhyay, Felix Glaser, Benjamin Elias, Quentin Michaudel, and Ludovic Troian-Gautier

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.5c22244
19 Feb 10:07

[ASAP] Nickel-Catalyzed Asymmetric Carboacylation of Alkenes via CO Transfer

by Wen Zhang, Man Wang, Shan Luo, Jinze Du, Xiang Lyu, Hequan Yao, and Yuli He

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.5c23037
13 Feb 15:32

[ASAP] Unraveling the Mechanism of a Co(−I)–Ga Photoreductant in the Catalytic Hydrodefluorination of Electron-Rich Fluoroarenes

by Francis Y. T. Lam, Michael J. Dorantes, Jacob Schaffner, Tom Bergmann, Maurice van Gastel, Gregor Schnakenburg, Victor G. Young, Jr., David A. Blank, and Connie C. Lu

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.5c16672
13 Feb 15:31

[ASAP] Expanding Ullmann Homocoupling to Cross-Coupling: Electrochemical Copper-Catalyzed Cross-Electrophile Coupling of Alkyl and Aryl Halides

by Kailun Liang, Yuhongxu Bai, Hang Li, Yingjie Li, Chengbiao Zhu, Zhenwei Wei, and Caiyou Chen

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.5c20694
09 Feb 12:02

[ASAP] Photoredox Unmasking of Aromatic C–H Bonds in Living Environments Enabled by Thianthrenium Salts

by Mauro Mato, Adrián Rivas-Saborido, Alba Casas-Pais, María Tomás-Gamasa, and José L. Mascareñas

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.6c00530
07 Feb 07:24

[ASAP] Leveraging Divergent Ligand-to-Metal Charge-Transfer Excited State Pathways for Catalyst Control over Alkoxyl Radical Reactivity

by Zilu Tang, Yetong Lin, Arshad Mehmood, Ashley E. Lojko, Jagrut A. Shah, Noah J. Schwartzapfel, Benjamin G. Levine, and Jeffrey M. Lipshultz

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.5c22609
07 Feb 07:22

[ASAP] Inverse Molecular Design for the Discovery of Organic Energy Transfer Photocatalysts: Bridging Global and Local Chemical Space Exploration

by Leon Schlosser, Nils H. Rendel, Julius Gemen, Frank Glorius, and Kjell Jorner

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.5c20087
07 Feb 07:21

[ASAP] Photodriven Enantioselective 6-endo Hydroaminative Cyclization to Chiral 4-Substituted 3,4-Dihydroisoquinolones

by Jiahao Zhang, Chaoren Shen, Zheng Huang, and Kaiwu Dong

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.5c16930