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18 Jul 07:34

[ASAP] Total Synthesis of (+)-Herpotrichones A–C

by Yoojin Lee, Taewan Kim, Geon Kim, Dongwook Kim, and Sunkyu Han

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.5c05061
18 Jul 07:33

Redox-powered autonomous directional C–C bond rotation under enzyme control

by Jordan Berreur

Nature, Published online: 16 July 2025; doi:10.1038/s41586-025-09291-6

A redox reaction network, comprising concurrent oxidation and reduction pathways, is described that can drive autonomous unidirectional motion about a C–C bond in a structurally simple synthetic molecular motor based on an achiral biphenyl.
18 Jul 07:32

Skeletal editing of pyrrolidines by nitrogen-atom insertion

by Jinghao Li, Pengcheng Tang, Yang Fan, Hongjian Lu
Science, Volume 389, Issue 6757, Page 275-281, July 2025.
18 Jul 07:30

Bridging the pyridine-pyridazine synthesis gap by skeletal editing

by Mikus Puriņš, Hikaru Nakahara, Mark D. Levin
Science, Volume 389, Issue 6757, Page 295-298, July 2025.
17 Jul 10:58

An Immobilized Rh‐Based Solid Molecular Catalyst for the Reductive Hydroformylation of 1‐Octene

by Keanu V. A. Birkelbach, Jeroen T. Vossen, Thorsten Rösler, Isabella Kappel, Ansgar Meise, Marc Heggen, Andreas J. Vorholt, Regina Palkovits
An Immobilized Rh-Based Solid Molecular Catalyst for the Reductive Hydroformylation of 1-Octene

In the center a greenish droplet made of marble can be seen from which a chemical structure emerges, exemplifying the presented heterogenized, but molecular catalyst system for the reductive hydroformylation. The catalyst design was inspired by a homogeneous Rh-predecessor, which can be seen in the back in a characteristic dark green. Surrounding the droplet of the best-performing catalyst are masonry tools and broken drops featuring previous, less effective catalyst design iterations. Details of this research are reported by Andreas J. Vorholt et al. in their Research Article (e202424144).


17 Jul 07:32

[ASAP] Electrochemically Driven Dearomative Spirocyclization of Anisole-Based Cyclopropanols: Total Synthesis of Anhydro-β-rotunol

by Shuai Lei, Zhaojun Ding, Yankun Zhao, Changhong Xie, Chenyang Wang, Jiayu Mo, and Min Zhang

TOC Graphic

Organic Letters
DOI: 10.1021/acs.orglett.5c02177
17 Jul 07:31

One-pot electrocatalytic lignin depolymerization with in situ extraction: a feasible approach for the production of biomass-based oils

Green Chem., 2025, 27,9927-9936
DOI: 10.1039/D5GC01810B, Paper
Lucie M. Lindenbeck, Silas Brand, Finn Schatz, Franka Stallmann, Nele Petersen, Björn B. Beele, Jessica Pichler, Marcella Frauscher, Raphaela Süss, Pascal Olschowski, Serhiy Budnyk, Adam Slabon, Bruno V. M. Rodrigues
A biphasic electrocatalytic system using MIBK extracts lignin-derived compounds during the aqueous-phase depolymerization of Kraft lignin, affording a stable, low-molecular-weight bio-oil (>60% yield) with potential as a lubricant base oil. Image partly generated using AI.
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16 Jul 11:24

[ASAP] Electrochemical Single-Carbon Insertion via Distonic Radical Cation Intermediates

by Tatsuya Morimoto, Yoshio Nishimoto, Taku Suzuki-Osborne, Su-Gi Chong, Kazuhiro Okamoto, Tomoki Yoneda, Azusa Kikuchi, Daisuke Yokogawa, Mahito Atobe, and Naoki Shida

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Journal of the American Chemical Society
DOI: 10.1021/jacs.5c06798
15 Jul 06:27

[ASAP] Asymmetric Total Syntheses of (−)-Ervatamine and (+)-19,20-Dehydroervatamine via Late-Stage Directed Indolization

by Qinyang Chen, Da-Yun Jeon, and Cheon-Gyu Cho

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Organic Letters
DOI: 10.1021/acs.orglett.5c01430
15 Jul 06:27

[ASAP] An Asymmetric Approach toward the Aristotelia Alkaloid (−)-Penduncularine

by Guoduan Liang, Kirsten E. Christensen, and Edward A. Anderson

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Organic Letters
DOI: 10.1021/acs.orglett.5c02062
14 Jul 14:39

[ASAP] Ligand Design Enables the Palladium-Catalyzed Intermolecular Carbochlorocarbonylation of Alkynes and Cyclopentenone Formation

by Elliott H. Denton, Hendrik L. Schmitt, Olivera Stepanović, Patrick Müller, Alexander F. Müller, Daniel Svoboda, and Bill Morandi

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Journal of the American Chemical Society
DOI: 10.1021/jacs.5c01707
14 Jul 14:33

The Overlooked Dual Phosphorescence of Lappert's Diamino Stannylene Sn[N(SiMe3)2]2

by Philipp Sikora, Robert Naumann, Lukas Sorge, Christoph Förster, Katja Heinze
The Overlooked Dual Phosphorescence of Lappert's Diamino Stannylene Sn[N(SiMe3)2]2

The diamino stannylene Sn[N(SiMe3)2]2 shows rich photophysics and photochemistry: unprecedented dual green/orange phosphorescence with long excited state lifetimes, excimer formation, and unimolecular bond homolysis. Photolytic Sn─N bond homolysis occurs only in the long-lived excited monomer but not in the excimer.


Abstract

The first stable heavy carbene homologues, the heavy tetrylenes, were reported in 1973 by Lappert and coworkers. These tetrylenes were extensively investigated with respect to ground state reactivity, such as small molecule activation, insertion into σ-bonds, coordination chemistry, materials chemistry, or catalysis. Their photophysical properties remained essentially unexplored. We report that the bright yellow-colored diamino stannylene Sn[N(SiMe3)2]2 shows thermally activated dual orange/green phosphorescence with microsecond lifetime in fluid solution at room temperature, which has been overlooked for more than 50 years. These unique electronic and photophysical properties are studied in detail by temperature-dependent time-resolved emission and absorption spectroscopy and are corroborated by (time-dependent) density functional theory (DFT) calculations. The mechanism of photochemical radical formation has been disclosed, involving unprecedented stannylene excimers with second-order Jahn–Teller distorted structures. The present study provides new insights toward a rational design of tetrel(II) complexes with long-lived emissive excited states, with Sn[N(SiMe3)2]2 being the prototype.

13 Jul 11:23

[ASAP] Pericyclic Umpolung in a Catalytic Asymmetric Diels–Alder Reaction of Tropone with Enol Ethers

by Tianyu Zheng, Zikuan Wang, Benjamin Mitschke, Nils Nöthling, Markus Leutzsch, Frank Neese, and Benjamin List

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Journal of the American Chemical Society
DOI: 10.1021/jacs.5c05709
11 Jul 20:07

[ASAP] [1,3]-Hydride Shift in α-Boryl Cations: Strategic Design of Fluorine-Triggered Cyclopropanation

by Seungcheol Han, Yeosan Lee, Jaeyoon Seo, Junseok Lee, and Seung Hwan Cho

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Journal of the American Chemical Society
DOI: 10.1021/jacs.5c08276
10 Jul 08:12

[ASAP] Stereodivergent Synthesis of Perhydrobenz[e]indene Terpenoids

by Cheng Yang, Christopher J. Huck, Yaroslav D. Boyko, Shang Ning, Uroš Vezonik, Alexander S. Shved, Scott E. Denmark, Binh Khanh Mai, and David Sarlah

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Journal of the American Chemical Society
DOI: 10.1021/jacs.5c07068
08 Jul 06:22

[ASAP] Deoxygenative [3 + 2] Annulation of α,β-Unsaturated Carbonyl Compounds and Electron-Rich Olefins via Photocatalytic Umpolung of Triarylphosphine

by Taiga Ando, Daisuke Yokogawa, Kohsuke Ohmatsu, and Takashi Ooi

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Journal of the American Chemical Society
DOI: 10.1021/jacs.5c06114
07 Jul 12:59

[ASAP] Asymmetric Total Synthesis of (−)-Lemnalemnane C

by Toyoharu Kobayashi, Rina Sugitate, Yuichiro Kawamoto, and Hisanaka Ito

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Organic Letters
DOI: 10.1021/acs.orglett.5c00649
07 Jul 11:15

[ASAP] Total Synthesis of Jerangolid B via sp3–sp2 Stille Coupling

by Janick Schug, Bernd Morgenstern, and Johann Jauch

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Organic Letters
DOI: 10.1021/acs.orglett.5c02569
03 Jul 14:33

[ASAP] Direct Generation of Carboxyl Radicals from Carboxylic Acids Catalyzed by Photoactivated Ketones

by Kenji Yamashita, Hayate Sano, Yuki Goto, Hiroki Hayashi, and Yoshitaka Hamashima

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Journal of the American Chemical Society
DOI: 10.1021/jacs.5c04571
03 Jul 09:11

Boron-mediated modular assembly of tetrasubstituted alkenes

by Liang Wei

Nature, Published online: 02 July 2025; doi:10.1038/s41586-025-09209-2

A method based on boron-mediated assembly is described for the synthesis of tetrasubstituted alkenes, molecules with four substituents around the central C=C bond, with complete control over the double-bond geometry.
01 Jul 15:10

Enantioselective electroreductive alkyne-aldehyde coupling

by Xiyang Cao

Nature Communications, Published online: 01 July 2025; doi:10.1038/s41467-025-60230-5

Electrocatalytic methods that enable asymmetric reductive coupling of two π-components with regio-, stereo-, and enantioselectivity control are underexplored. Here, the authors report a regio- and enantioselective cobaltaelectro-catalyzed alkyne-aldehyde coupling reaction, in which protons and electrons serve as the hydrogen source and reductant, respectively.
01 Jul 15:09

[ASAP] Asymmetric Synthesis of Unnatural (−)-Gracilamine

by Maxime Denis and Sylvain Canesi

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Organic Letters
DOI: 10.1021/acs.orglett.5c02377
01 Jul 15:07

[ASAP] Regiodivergent α- and β-Functionalization of Saturated N-Heterocycles by Photocatalytic Oxidation

by Jonas W. Rackl, Alexander F. Müller, Antonia Profyllidou, and Helma Wennemers

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Journal of the American Chemical Society
DOI: 10.1021/jacs.5c06177
01 Jul 15:05

[ASAP] Total Synthesis of Daphenylline via Diels–Alder Cycloaddition and Rhodium-Catalyzed C–H Alkynylation

by Wei Chen, Aohang Liu, Jinwei Huang, Pengfei Yu, Huaxuan Zhang, Huilin Li, Xingang Xie, Gaoyuan Zhao, and Xuegong She

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Organic Letters
DOI: 10.1021/acs.orglett.5c02227
01 Jul 15:05

[ASAP] Radical Sorting Catalysis via Bimolecular Homolytic Substitution (SH2): Opportunities for C(sp3)–C(sp3) Cross-Coupling Reactions

by Iona M. McWhinnie, Robert T. Martin, Jiaxin Xie, Ruizhe Chen, Cesar N. Prieto Kullmer, and David W. C. MacMillan

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Journal of the American Chemical Society
DOI: 10.1021/jacs.5c07367
01 Jul 13:02

Boryl Radical beta-Scission Enables Divergent Deaminative Cross-Coupling of Amines

by Daniele, Leonori
Amines are among the most common functional groups in bioactive molecules and pharmaceuticals, yet they are almost universally treated as synthetic endpoints. Here we report a strategy that repositions native primary, secondary, and tertiary amines as versatile handles for divergent cross-coupling. The platform relies on in situ activation via borane coordination and exploits a copper catalytic redox system that generates amine-ligated boryl radicals, which undergo beta-scission across the C(sp³)–N bond to release alkyl radicals. These intermediates engage in copper-catalyzed cross-couplings with a broad array of C-, N-, O-, and S-based nucleophiles. The method tolerates diverse amine classes, enables modular functionalization, and supports late-stage editing of complex drug scaffolds. In addition, amides can be incorporated into the manifold via reductive funneling. This work establishes a general approach to deaminative C–N bond functionalization and introduces a new logic for retrosynthetic diversification and pharmacophore remodeling.
30 Jun 10:37

Ligand‐Controlled Chemoselectivity in the Rhodium‐Catalyzed Synthesis of Pentafulvenes via (2 + 2 + 1) Alkyne Cyclotrimerization

by Belinda Español‐Sánchez, Jesús Moradell, María Galiana‐Cameo, Eduardo Barrenas, Jesús J. Pérez‐Torrente, Vincenzo Passarelli, Ricardo Castarlenas
Ligand-Controlled Chemoselectivity in the Rhodium-Catalyzed Synthesis of Pentafulvenes via (2 + 2 + 1) Alkyne Cyclotrimerization

Chemoselectivity Challenge: A precise catalyst design allows for chemoselectivity control over alkyne reactivity to yield pentafulvenes via (2 + 2 + 1) cyclotrimerization. Operative mechanism has been elucidated by means of stoichiometric and deuteration experiments, as well as DFT calculations.


Abstract

The synthesis of pentafulvenes with varied substituents has been efficiently achieved using novel rhodium-based catalysts via (2 + 2 + 1) alkyne cyclotrimerization. A rational design of the catalyst structure, including pyridonato, NHC, and CO ligands, ensures the alkyne chemoselectivity and prevents the formation of robust rhodium-fulvene species. Furthermore, the judicious choice of acidity and steric properties of different alkynes enables the preparation of cross-coupled fulvene derivatives. Stoichiometric and deuteration experiments, as well as DFT calculations, shed light on the reaction mechanism, showing that it includes an initial alkyne deprotonation, two successive alkyne insertions, cyclization, and protonolysis, the first insertion being the rate-determining step.

30 Jun 10:36

Transform the World through Chemistry

by Paul T. Anastas, Walter Leitner
Angewandte Chemie International Edition, Volume 64, Issue 33, August 11, 2025.
27 Jun 09:19

[ASAP] Gram-Scale Total Synthesis of Illisimonin A

by Liangchao Zhu, Jinrui Li, and Zhaohong Lu

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.5c07921
27 Jun 09:19

Carbonyl-to-sulfur swap enabled by sequential double carbon-carbon bond activation

by Zining Zhang and Guangbin Dong
Science, Volume 388, Issue 6754, Page 1436-1440, June 2025.