03 Jun 13:21
by Neetu Sharma,
Yanyao Liu,
Partha Sarathi Hazra,
Evan B. Piper,
Ryan Van Hoveln,
Michael Kevin Brown
An oxa-boracycle conformational lock strategy enables photocatalytic [2+2] cycloaddition to afford densely substituted cyclobutylboronates. The conformational constraint suppresses triplet relaxation and promotes productive bimolecular reactivity. Divergent oxidation conditions provide access to either 1,5-dicarbonyls or cyclobutanols, and the synthetic utility of the products was further demonstrated through C─B bond functionalization.
ABSTRACT
The De Mayo reaction is an established process in chemical synthesis for the synthesis of 1,5-dicarbonyls or cyclobutanols in selected cases. Herein, we present a reevisioned approach that utilizes alkenylboronates as surrogates for 1,3-dicarbonyls. The process allows for delayed controlled synthesis of the traditional De Mayo products. Elaboration of the C─B bond in the product was also demonstrated. A key aspect of the study is the identification of a rigid oxy-boracycle as a key intermediate to allow for bimolecular cycloaddition to occur. Mechanistic experiments are provided to clarify the importance of the chelate.
01 Jun 12:49
Chem. Sci., 2026, Accepted Manuscript
DOI: 10.1039/D6SC03309A, Edge Article
Open Access
Qiang Liu, Chenxu Yan, Xie Li, Haiyang Huang, Zheyu Fan, Jizhan Zhang, Weiwei Zhang, Ping Shi, Yuzheng Zhao, Zhiqian Guo, Weihong Zhu
Hydroxyl radical (•OH), the most potent reactive oxygen species, plays a crucial role in photodynamic therapy (PDT). However, conventional photosensitizers (PSs) produce •OH through the classical Haber-Weiss pathway suffer from...
The content of this RSS Feed (c) The Royal Society of Chemistry
27 May 08:19
by Isabelle Cai, Sara M. Guzman, Joshua S. Derasp, Maria Victoria Silva Elipe, James I. Murray, and Jason E. Hein
ACS Catalysis
DOI: 10.1021/acscatal.6c00650
12 May 07:15
Chem. Sci., 2026, Advance Article
DOI: 10.1039/D6SC00960C, Review Article
Open Access
Jiao He, Perla Bharath Kumar, Yulong Li, Qiong Yu, Wei Shu
Nickel-catalysed hydrofunctionalization of alkenes constructs stereogenic centres by C(sp3)–C(sp3) cross-coupling. This review highlights recent advances in recent advances in this area, focusing on strategy development, mechanistic considerations.
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The content of this RSS Feed (c) The Royal Society of Chemistry
10 May 06:49
by Jiawei Li,
Xiao Xiao,
Qi Yang,
Baoguo Zhao,
Sanzhong Luo
To rigorously define reaction generality in organic synthesis, be a cartographer, not a hunter. ScopeMap transforms substrate assessment into a precise boundary mapping exercise. Unlike static optimization methods, this dynamic pipeline leverages geometric repulsion and manual feedback to actively probe structural cliffs. It enables the efficient discovery of synthetic limitations and provides standardized metrics (U-Score/R-Score) for rigorous scope evaluation.
ABSTRACT
Assessing the generality of synthetic methods is a cornerstone of organic chemistry, yet traditional manual selection and current optimization-driven algorithms often fail to delineate reaction boundaries, clustering instead in high-reactivity regions. Herein, we introduce ScopeMap, an iterative, human-in-the-loop workflow designed to efficiently map functional limits rather than merely maximizing performance. Leveraging a modified Centroidal Voronoi Tessellation (CVT) algorithm with a dynamic geometric repulsion potential, ScopeMap transforms negative experimental feedback into geometric constraints, actively steering sampling toward unexplored frontiers. Validated against a comprehensive dataset of biomimetic aldol reactions and a cobalt-catalyzed coupling system, the workflow achieves greater substrate diversity with a smaller selection of examples. By utilizing a representative subset comprising fewer than 4% of the substrate space, it successfully predicts the reactivity of the reaction space with an F1 score exceeding 90%. Furthermore, we establish the U-Score and R-Score—metrics derived from spatial entropy and mean squared distance (MSD)—to provide a standardized framework for quantifying sampling uniformity and representativeness. This work offers a resource-efficient paradigm for defining reaction generality, shifting the focus from exhaustive data enumeration to information-dense boundary mapping.
10 May 06:47
by Sergio M. Bonesi, Andrea Casagrande, Andrea Lapi, Michela Salamone, Davide Ravelli, Osvaldo Lanzalunga, Massimo Bietti, and Maurizio Fagnoni
ACS Catalysis
DOI: 10.1021/acscatal.6c02037
10 May 06:47
by George D. Johnson, Stephanie A. Corio, James D. Grayson, Joshua D. Tibbetts, George Ballantyne, Qiao Cao, Hannah E. Askey, Joseph J. Bell-Tyrer, Oleksandr P. Datsenko, Mark A. Graham, Pavel K. Mykhailiuk, Jennifer S. Hirschi, and Alexander J. Cresswell
ACS Catalysis
DOI: 10.1021/acscatal.6c01036
10 May 06:37
by William Y. Zhao, Noriyuki Takanashi, Albert Cabré, Joseph R. Martinelli, and David W. C. MacMillan
Journal of the American Chemical Society
DOI: 10.1021/jacs.6c04676
10 May 06:33
by Fangjia Zhang, Tilong Yang, Zhongming Cheng, Pinhong Chen, Zhenyang Lin, and Guosheng Liu
Journal of the American Chemical Society
DOI: 10.1021/jacs.6c05474
10 May 06:32
by Nya E. Black, Dara Cheng, Brandon P. Grasty, and Dylan G. Boucher
Journal of the American Chemical Society
DOI: 10.1021/jacs.5c20952
10 May 06:31
Chem. Sci., 2026, Advance Article
DOI: 10.1039/D6SC02413K, Edge Article
Open Access
Nathan M. Alcock, Myron S. Huzan, Timothy G. Burrow, Myrtille O. J. Y. Hunault, Christelle Tamain, Matthieu Autillo, Thomas Dumas, Michael L. Baker
Early actinide covalency trends are revealed, and sensitivity to inner versus outer components of the 5f radial wavefunction is determined by 3d4f resonant inelastic X-ray scattering.
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The content of this RSS Feed (c) The Royal Society of Chemistry
10 May 06:30
Chem. Sci., 2026, Advance Article
DOI: 10.1039/D6SC02111E, Edge Article
Open Access
Alexandra Matei, Baptiste Roure, Xiaobing Chen, Sebastian B. Beil, Ben L. Feringa
Lucigenin, a widely used fluorescent probe in biology, was used for the first time in photocatalysis to achieve the direct C–H azolation of arenes.
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The content of this RSS Feed (c) The Royal Society of Chemistry
10 May 06:29
Chem. Sci., 2026, Advance Article
DOI: 10.1039/D6SC00358C, Edge Article
Open Access
Xi Zhang, Jingyi Bai, Yue Zhao, Minyan Wang, Zhuangzhi Shi
A P(III)-directed C–H arylation method has been established, enabling the modular assembly of biaryl phosphoramidite (BPA) libraries that demonstrated exceptional efficacy in palladium-catalyzed asymmetric reactions.
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The content of this RSS Feed (c) The Royal Society of Chemistry
06 May 08:22
by Pei-Pei He, Hua-Wei Liu, Tianshuai Zhu, Zupeng Chen, and Zhen Chen
ACS Catalysis
DOI: 10.1021/acscatal.6c01870
06 May 08:21
by Yu‐Shan Zhang,
Bing Zhong,
Likun Dong,
Jin‐Dong Yang,
Jin‐Pei Cheng
Diazaphosphinyl radicals are exploited as catalysts that favor catalytic hydrodehalogenation of alkyl chlorides over bromides/iodides. Mechanistic studies reveal the pivotal role of polar steps in governing radical-catalysis selectivity. The catalyst enables selective mono-dechlorination of dichlorides, and facilitates hydroalkylation of activated olefins, offering a sustainable, metal-free strategy for valorizing chlorides.
ABSTRACT
Catalytic radical halogen atom transfer (XAT) typically follows the bond dissociation free energy (BDFE)-dependent reactivity order R–I > R–Br > R–Cl, leaving abundant alkyl chlorides largely underutilized. We report diazaphosphinyl radicals (NHP•) derived from N-heterocyclic phosphines as efficient organic radical catalysts that invert this trend, enabling catalytic hydrodehalogenation of alkyl chlorides over bromides and iodides. Comprehensive thermodynamic, kinetic, and mechanistic studies reveal dual roles of NHP derivatives: XAT abstractors and hydrogen donors. The overall catalytic efficiency is governed not by the radical XAT step, but by a polar bond-metathesis process that regenerates the active P-H reductant (NHP-H). This step is thermodynamically much favorable for chlorides, due to the strong Si–Cl bond formed, thereby establishing a closed catalytic cycle uniquely effective for R–Cl substrates. The catalyst exhibits good functional-group tolerance and enables mono-dechlorination of dichlorides with high selectivity, as well as hydroalkylation of activated olefins. This work highlights the important roles of polar steps in radical catalysis that can dictate substrate selectivity, and provides a sustainable, metal-free strategy for valorizing alkyl chlorides.
30 Apr 05:48
by P. Scott Pedersen, Katherine I. Burton, Sven H. M. Kaster, Eva Lin, Andria L. Pace, Marian C. Bryan, Taylor M. Sodano, Nicholas E. Intermaggio, Christopher B. Kelly, and David W. C. MacMillan
Journal of the American Chemical Society
DOI: 10.1021/jacs.5c21614
27 Apr 19:47
Chem. Sci., 2026, 17,10729-10734
DOI: 10.1039/D6SC00657D, Edge Article
Open Access
Duc An Truong, Soichiro Mori, Taiki Ninomiya, Ryoya Niwa, Bumpei Maeda, Haruka Fujino, Masayuki Inoue, Kohsuke Ohmatsu, Takashi Ooi
The direct generation of carbon radicals from carboxylic acids under visible-light photocatalysis offers an appealing strategy for molecular diversification.
The content of this RSS Feed (c) The Royal Society of Chemistry
27 Apr 19:45
Chem. Sci., 2026, Advance Article
DOI: 10.1039/D6SC01846G, Edge Article
Open Access
Daniel A. Santos Oliveira, Daniela Rodrigues Silva, Ataualpa A. C. Braga, Célia Fonseca Guerra, Robin N. Perutz, Odile Eisenstein, F. Matthias Bickelhaupt
A reduction in Pauli repulsion is the major determinant of increased bond dissociation energy on fluorine substitution, with an additional contribution from orbital interactions required to account for the ortho selectivity.
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The content of this RSS Feed (c) The Royal Society of Chemistry
27 Apr 19:42
by Anthony R. Scavuzzo, Justin E. Garza, and Brad P. Carrow
Organometallics
DOI: 10.1021/acs.organomet.6c00016
27 Apr 19:39
by Hui Xu, Shuaiqi Lu, Zhenzhen Li, Zhengjun He, Yongxin Zhang, Jiang Duan, Ligang Huang, Lijun Jiang, and Chao Shu
ACS Catalysis
DOI: 10.1021/acscatal.6c00501
21 Apr 12:55
Chem. Sci., 2026, Advance Article
DOI: 10.1039/D6SC01462C, Edge Article
Open Access
Robert J. Ortiz, Dion B. Nemez, Mahtasim Bhuiyan, Keighlynn A. Veilleux, David E. Herbert
The first examples of deep-red Ir(III)-mediated photochemistry are reported, via direct excitation into the triplet manifold of an iridium coordination complex of a benzannulated biphenanthridine ligand scaffold using 740 nm light.
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The content of this RSS Feed (c) The Royal Society of Chemistry
21 Apr 12:50
by Sheng Ye, Kangyue Shi, Hongbo Ouyang, Haojun Hu, Zihan Yu, Ting Cheng, and Zhikun Zhang
ACS Catalysis
DOI: 10.1021/acscatal.6c01555
21 Apr 10:11
by Zhenzhong Liu, Yijun Liu, Lejuan Cai, Guangtao Ma, Jiawei Li, Yuquan Ding, Aobo Chen, Nana Wang, Jian Shang, Jingxiang Low, Askar Parmanov, Olim Ruzimuradov, Ning Zhang, and Yujie Xiong
Journal of the American Chemical Society
DOI: 10.1021/jacs.6c01267
02 Apr 16:46
by Thomas M. Hood, Sophie H. Dewick, Anjali John, Jeremiah P. Tidey, Julie V. Macpherson, Ragnar Bjornsson, Emma Richards, Tobias Krämer, and Adrian B. Chaplin
Organometallics
DOI: 10.1021/acs.organomet.6c00053
02 Apr 16:45
by Daniel Hupperich, Theresa Sperger, Eirik Lyngvi, and Franziska Schoenebeck
Organometallics
DOI: 10.1021/acs.organomet.6c00023
02 Apr 16:43
by Ying Hua, En Luo, and Jie Liu
Journal of the American Chemical Society
DOI: 10.1021/jacs.6c03357
02 Apr 16:43
by Chao Xu, Yuanrui Wang, Guang Zeng, and Xiao-Feng Wu
Journal of the American Chemical Society
DOI: 10.1021/jacs.6c03507
02 Apr 16:41
by Daniela Carmona-Pérez, William W. Brennessel, and Agnes E. Thorarinsdottir
Journal of the American Chemical Society
DOI: 10.1021/jacs.5c21444
02 Apr 16:40
by Taemin Kim, Ching-Nung Chen, and Anna Wuttig
Journal of the American Chemical Society
DOI: 10.1021/jacs.5c22765
26 Mar 19:12
by Matthew T. Zambri, Matthew H. L. Chow, and Mark S. Taylor
ACS Catalysis
DOI: 10.1021/acscatal.6c00713
