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Unlocking a (Pseudo)‐Mechanically Interlocked Molecule with a Coronene “Shoehorn”

Unlocking a (Pseudo)-Mechanically Interlocked Molecule with a Coronene “Shoehorn”

A mechanically interlocked molecule (MIM) comprising a tetragold metallobox and a tetraoctynyl-pyrene guest that can be regarded as a pseudo-metallosuit[4]ane is described. In contrast to other MIMs, the tetrasubstituted guest can be released from this molecule by the addition of coronene through a “shoehorning” mechanism.

Abstract

Mechanically interlocked molecules (MIMs) have gained increasing interest during the last decades, not only because of their aesthetic appeal, but also because their unique properties have allowed them to find applications in nanotechnology, catalysis, chemosensing and biomedicine. Herein we describe how a pyrene molecule with four octynyl substituents can be easily encapsulated within the cavity of a tetragold(I) rectangle-like metallobox, by template formation of the metallo-assembly in the presence of the guest. The resulting assembly behaves as a mechanically interlocked molecule (MIM), in which the four long limbs of the guest protrude from the entrances of the metallobox, thus locking the guest inside the cavity of the metallobox. The new assembly resembles a metallo-suit[4]ane, given the number of protruding long limbs and the presence of the metal atoms in the host molecule. However, unlike normal MIMs, this molecule can release the tetra-substituted pyrene guest by the addition of coronene, which can smoothly replace the guest in the cavity of the metallobox. Combined experimental and computational studies allowed the role of the coronene molecule in facilitating the release of the tetrasubstituted pyrene guest to be explained, through a process that we named “shoehorning”, as the coronene compresses the flexible limbs of the guest so that it can reduce its size to slide in and out the metallobox.

Wiley: Angewandte Chemie International Edition: Table of Contents
Authors: Susana Ibáñez, Katarzyna Świderek, Eduardo Peris
onlinelibrary.wiley.com/doi/10.1002/anie.202301914

N‐(Morpholine‐4‐dithio)phthalimide: A Shelf‐Stable, Bilateral Platform Molecule Enabling Access to Diverse Unsymmetrical Disulfides

N-(Morpholine-4-dithio)phthalimide: A Shelf-Stable, Bilateral Platform Molecule Enabling Access to Diverse Unsymmetrical Disulfides**

A shelf-stable and easy-to-prepare disulfurating reagent with chemoselectively displaceable amino and imide leaving groups is described. Protonation of this reagent promotes exclusive displacement of the amino group with various neutral carbon nucleophiles. The resulting dithiophthalimides are amenable to diverse substitution reactions under basic or neutral conditions, thus enabling expedient access to structurally diverse unsymmetrical disulfides.

Abstract

Synthetic methods for unsymmetrical disulfides are greatly needed owing to their applications in drug discovery, linker chemistry, and materials sciences. In this study, a new shelf-stable and easy-to-prepare bilateral disulfurating platform molecule, N-(morpholine-4-dithio)phthalimide, has been developed for the divergent synthesis of unsymmetrical disulfides. The amino and imide leaving groups of this reagent can be orthogonally transformed. Under acidic conditions, the amino moiety undergoes selective protonation and thus can be displaced by various carbon nucleophiles, such as allyl trimethylsilanes, alkynyl silanes, and electron-rich arenes, leaving the phthalimide moiety untouched. Meanwhile, the phthalimide leaving group is amenable to substitution under basic or neutral conditions. The combination of these transformations provides rapid access to diverse unsymmetrical disulfides through two C−S bond-forming reactions.

Wiley: Angewandte Chemie International Edition: Table of Contents
Authors: Hayato Asanuma, Kazuya Kanemoto, Tokiharu Watanabe, Shin‐ichi Fukuzawa
onlinelibrary.wiley.com/doi/10.1002/anie.202219156

Facile Synthesis and Chiral Resolution of Expanded Helicenes with up to 35 cata‐Fused Benzene Rings

Facile Synthesis and Chiral Resolution of Expanded Helicenes with up to 35 cata-Fused Benzene Rings**

Expanded helicenes with up to 35 cata-fused benzene rings can be synthesized by Suzuki-coupling-mediated oligomerization followed by bismuth(III)-triflate-catalyzed cyclization of vinyl ethers. Their chiroptical properties were also studied.

Abstract

Expanded helicenes are expected to show enhanced chiroptical properties as compared to the classical helicenes but the synthesis is very challenging. Herein, we report the facile synthesis of a series of expanded helicenes Hn (n=1–4) containing 11, 19, 27 and 35 cata-fused benzene rings through Suzuki coupling-based oligomerization followed by Bi(OTf)3-mediated regioselective cyclization of vinyl ethers. Their structures were determined by X-ray crystallographic analysis. Enantiopure H2, H3, and H4 can be isolated by chiral HPLC and they all exhibit strong chiroptical responses with high absorption dissymmetry factor (|gabs|) values (0.020 for H2, 0.021 for H3, and 0.021–0.024 for H4).

Wiley: Angewandte Chemie International Edition: Table of Contents
Authors: Gui‐Fei Huo, Toshiya M. Fukunaga, Xudong Hou, Yi Han, Wei Fan, Shaofei Wu, Hiroyuki Isobe, Jishan Wu
onlinelibrary.wiley.com/doi/10.1002/anie.202218090

Modular Synthesis of a Tridecasaccharide Motif of Bacteroides vulgatus Lipopolysaccharides against Inflammatory Bowel Diseases through an Orthogonal One‐Pot Glycosylation Strategy

Modular Synthesis of a Tridecasaccharide Motif of Bacteroides vulgatus Lipopolysaccharides against Inflammatory Bowel Diseases through an Orthogonal One-Pot Glycosylation Strategy

A tridecasaccharide from Bacteroides vulgatus mpk lipopolysaccharides has been synthesized for the first time by a strategy involving orthogonal one-pot glycosylation reactions based on glycosyl ortho-(1-phenylvinyl)benzoates, which precluded issues such as aglycone transfer and the unpleasant odor of thioglycoside-based orthogonal one-pot glycosylation.

Abstract

Lipopolysaccharides from Bacteroides vulgatus represent interesting targets for the treatment of inflammatory bowel diseases. However, efficient access to long, branched and complex lipopolysaccharides remains challenging. Herein, we report the modular synthesis of a tridecasaccharide from Bacteroides vulgates through an orthogonal one-pot glycosylation strategy based on glycosyl ortho-(1-phenylvinyl)benzoates, which avoids the issues of thioglycoside-based one-pot synthesis. Our approach also features: 1) 5,7-O-di-tert-butylsilylene-directed glycosylation for stereoselective construction of the α-Kdo linkage; 2) hydrogen-bond-mediated aglycone delivery for the stereoselective formation of β-mannosidic bonds; 3) remote anchimeric assistance for stereoselective assembly of the α-fucosyl linkage; 4) several orthogonal one-pot synthetic steps and strategic use of orthogonal protecting groups to streamline oligosaccharide assembly; 5) convergent [1+6+6] one-pot synthesis of the target.

Wiley: Angewandte Chemie International Edition: Table of Contents
Authors: Yunqin Zhang, Leilei Wang, Qingli Zhou, Zuoshan Li, Dan Li, Caixia Yin, Xiufang Wang, Guozhi Xiao
onlinelibrary.wiley.com/doi/10.1002/anie.202301351

An n‐Type Polythiophene Derivative with Excellent Thermoelectric Performance

An n-Type Polythiophene Derivative with Excellent Thermoelectric Performance

An n-type non-fused-ring conjugated polymer is developed by introducing electron-withdrawing imide or cyano groups to each thiophene unit of polythiophene backbone. The resultant polymer shows low LUMO/HOMO energy levels and highly ordered crystallite structure, leading to excellent thermoelectric performance after n-doping.

Abstract

Typical n-type conjugated polymers are based on fused-ring electron-accepting building blocks. Herein, we report a non-fused-ring strategy to design n-type conjugated polymers, i.e. introducing electron-withdrawing imide or cyano groups to each thiophene unit of a non-fused-ring polythiophene backbone. The resulting polymer, n-PT1, shows low LUMO/HOMO energy levels of −3.91 eV/−6.22 eV, high electron mobility of 0.39 cm2 V−1 s−1 and high crystallinity in thin film. After n-doping, n-PT1 exhibits excellent thermoelectric performance with an electrical conductivity of 61.2 S cm−1 and a power factor (PF) of 141.7 μW m−1 K−2. This PF is the highest value reported so far for n-type conjugated polymers and this is the first time for polythiophene derivatives to be used in n-type organic thermoelectrics. The excellent thermoelectric performance of n-PT1 is due to its superior tolerance to doping. This work indicates that polythiophene derivatives without fused rings are low-cost and high-performance n-type conjugated polymers.

Wiley: Angewandte Chemie International Edition: Table of Contents
Authors: Sihui Deng, Changshuai Dong, Jian Liu, Bin Meng, Junli Hu, Yang Min, Hongkun Tian, Jun Liu, Lixiang Wang
onlinelibrary.wiley.com/doi/10.1002/anie.202216049

Multi‐Stimuli Responsive Luminescence and Domino Phase Transition of Hybrid Copper Halides with Nonlinear Optical Switching Behavior

Multi-Stimuli Responsive Luminescence and Domino Phase Transition of Hybrid Copper Halides with Nonlinear Optical Switching Behavior

A multi-stimuli responsive luminescent material has been developed that not only exhibits reversible photoluminescence conversion and nonlinear optical switching in response to thermal stimulus, but also observes peculiar crystal-phase-recognition induced domino-type single-crystal-to-single-crystal phase transition and mechanical force induced phase transition under concomitant emission-color change.

Abstract

Although phase transition materials (PTMs) under external stimuli are of great research interest duo to their rich potential applications, it is still challenging to explore multi-responsive PTMs. Herein, two different phases of organic–inorganic hybrid copper-based halides, α- and β-Gua3Cu2I5 (Gua+=CN3H6+), were synthesized by solvent evaporation method, which they crystalize in the noncentrosymmetric space group Fdd2 with zero-dimensional structure and centrosymmetric space group C2/c with one-dimensional metal-halogen framework, respectively. Interestingly, it is firstly demonstrated that Gua3Cu2I5 simultaneously possesses reversible PL conversion and NLO switching properties in response to thermal stimulus. Strikingly, apart from heat, its structural phase transition can also be triggered by crystalline-phase-recognition (CPR) and mechanical force. These new findings may pave a path for future exploration of PTMs with multiple physical properties.

Wiley: Angewandte Chemie International Edition: Table of Contents
Authors: Jiajing Wu, Yue Guo, Jing‐Li Qi, Wen‐Dong Yao, Su‐Xin Yu, Wenlong Liu, Sheng‐Ping Guo
onlinelibrary.wiley.com/doi/10.1002/anie.202301937

Novel Indole–Chalcone Derivative-Ligated Platinum(IV) Prodrugs Attenuate Cisplatin Resistance in Lung Cancer through ROS/ER Stress and Mitochondrial Dysfunction

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Journal of Medicinal Chemistry

Journal of Medicinal Chemistry: Latest Articles (ACS Publications)
Authors: Zhikun Liu, Meng Wang, Rizhen Huang, Tianhui Hu, Yi Jing, Xiaochao Huang, Weiwei Hu, Guoxiu Cao, and Hengshan Wang
dx.doi.org/http://dx.doi.org/10.1021/acs.jmedchem.2c02036

Alternative Approach to the Large-Scale Synthesis of the Densely Functionalized Pyrrolidone BMT-415200

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Organic Process Research & Development
Organic Process Research & Development: Latest Articles (ACS Publications)

Authors: Souvik Rakshit, Shunmugaraj Sathasivam, Raghurami Reddy, Saladi V. Rao, Vijaykumar Shekarappa, Moorthy Kandasamy, Mohamed Jaleel, Saravanan Murugan, Anuradha Bhat, Tamilarasan Subramani, Thirumalai Lakshminarasimhan, Aravind Gangu, Steven R. Wisniewski, Nathaniel Kopp, Ian Hale, Jason M. Stevens, Victor W. Rosso, Martin D. Eastgate, and Rajappa Vaidyanathan
dx.doi.org/https://doi.org/10.1021/acs.oprd.3c00007

Asymmetric Synthesis of Spiropyrazolone-Fused Dihydrofuran-naphthoquinones Bearing Contiguous Stereocenters via a Michael Addition/Chlorination/Nucleophilic Substitution Sequence

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The Journal of Organic Chemistry

The Journal of Organic Chemistry: Latest Articles (ACS Publications)
Authors: Gaihui Li, Hongyu Zhang, Guoshun Zhang, Bei Wei, Bin Liu, Heng Song, Qingshan Li, and Shurong Ban
dx.doi.org/https://doi.org/10.1021/acs.joc.2c03013

Synthetic Access to a Framework-Stabilized and Fully Sulfided Analogue of an Anderson Polyoxometalate that is Catalytically Competent for Reduction Reactions

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Journal of the American Chemical Society

Journal of the American Chemical Society: Latest Articles (ACS Publications)
Authors: Jiaxin Duan, Hafeera Shabbir, Zhihengyu Chen, Wentuan Bi, Qin Liu, Jingyi Sui, Luka Đorđević, Samuel I. Stupp, Karena W. Chapman, Alex B. F. Martinson, Alice Li, Richard D. Schaller, Subhadip Goswami, Rachel B. Getman, and Joseph T. Hupp
dx.doi.org/https://doi.org/10.1021/jacs.2c12992

Structure-Based Design of Y‑Shaped Covalent TEAD Inhibitors

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Journal of Medicinal Chemistry

Journal of Medicinal Chemistry: Latest Articles (ACS Publications)
Authors: Wenchao Lu⧫, Mengyang Fan⧫, Wenzhi Ji⧫, Jason Tse, Inchul You, Scott B. Ficarro, Isidoro Tavares, Jianwei Che, Audrey Y. Kim, Xijun Zhu, Andrew Boghossian, Matthew G. Rees, Melissa M. Ronan, Jennifer A. Roth, Stephen M. Hinshaw, Behnam Nabet, Steven M. Corsello, Nicholas Kwiatkowski, Jarrod A. Marto, Tinghu Zhang, and Nathanael S. Gray
dx.doi.org/http://dx.doi.org/10.1021/acs.jmedchem.2c01548

Discovery of Nanomolar DCAF1 Small Molecule Ligands

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Journal of Medicinal Chemistry

Journal of Medicinal Chemistry: Latest Articles (ACS Publications)
Authors: Alice Shi Ming Li&, Serah Kimani&, Brian Wilson&, Mahmoud Noureldin, Héctor González-Álvarez, Ahmed Mamai, Laurent Hoffer, John P. Guilinger, Ying Zhang, Moritz von Rechenberg, Jeremy S. Disch, Christopher J. Mulhern, Belinda L. Slakman, John W. Cuozzo, Aiping Dong, Gennady Poda, Mohammed Mohammed, Punit Saraon, Manish Mittal, Pratik Modh, Vaibhavi Rathod, Bhashant Patel, Suzanne Ackloo, Vijayaratnam Santhakumar, Magdalena M Szewczyk, Dalia Barsyte-Lovejoy, Cheryl H. Arrowsmith, Richard Marcellus, Marie-Aude Guié, Anthony D. Keefe, Peter J. Brown, Levon Halabelian, Rima Al-awar, and Masoud Vedadi
dx.doi.org/http://dx.doi.org/10.1021/acs.jmedchem.2c02132

On the Discrepancy between Local and Average Structure in the Fast Na+ Ionic Conductor Na2.9Sb0.9W0.1S4

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Journal of the American Chemical Society

Journal of the American Chemical Society: Latest Articles (ACS Publications)
Authors: Oliver Maus, Matthias T. Agne, Till Fuchs, Paul S. Till, Björn Wankmiller, Josef Maximilian Gerdes, Rituraj Sharma, Michael Heere, Niina Jalarvo, Omer Yaffe, Michael Ryan Hansen, and Wolfgang G. Zeier
dx.doi.org/https://doi.org/10.1021/jacs.2c11803