Palladium-Catalyzed External-CO-Free Carbonylation of Aryl Bromides Using 2,4,6-Trichlorophenyl Formate

Konishi, Hideyuki; Sekino, Tomoyuki; Manabe, Kei

doi:10.1248/cpb.c18-00042

Cited by 8 publications

(4 citation statements)

References 32 publications

(27 reference statements)

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“…Syntheses of symmetric R–BQQDI derivatives were achieved on the basis of a reported procedure for BQQ using 1,5-dinitroanthraquinone as the starting material (Scheme ). A key precursor for the final product, BQQ–TCDA , was mediated by functionalization with four ester groups including two highly electrophilic aryl esters ( BQQ–TC ). The reaction of BQQ–TCDA with the target primary amine in the presence of propionic acid afforded R–BQQDI .…”

Section: Design and Synthesis Of Bqqdi For Enhanced 2d Characteristicsmentioning

confidence: 99%

Nitrogen-Containing Perylene Diimides: Molecular Design, Robust Aggregated Structures, and Advances in n-Type Organic Semiconductors

et al. 2022

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Metrics & MoreArticle Recommendations CONSPECTUS: Organic semiconductors (OSCs) have attracted much attention because of their potential applications for flexible and printed electronic devices and thus have been extensively investigated in a variety of research fields, such as organic chemistry, solid-state physics, and device physics and engineering. Organic thin-film transistors (OTFTs), a class of OSC-based devices, have been expected to be an alternative of silicon-based metal oxide semiconductor field-effect transistors (MOS-FETs), which is the indispensable element for most of the current electronic devices. However, the noncovalently aggregated, van der Waals solid nature of the OSCs, by contrast to covalently bound silicon, conventionally exhibits lower carrier mobilities, limiting the practical applications of OTFTs. In particular, electron-transporting (i.e., n-type) OSCs lag behind their hole-transporting (p-type) counterparts in carrier mobility and ambient stability as OTFTs. This is primarily because of the difficulty in achieving compatibility between the aggregated structure exhibiting excellent carrier mobility and that with enough electron affinity. Recent understandings of carrier transport in OSCs explain that large and two-dimensionally isotropic transfer integrals coupled with small fluctuations are crucial for high carrier mobilities. In addition, from a practical point of view, the compatibility with practical device processes is highly required. Rational molecular design principles, therefore, are still demanded for developing OSCs and OTFTs toward high-end device applications. Herein, we will show our recent progress in the development of n-type OSCs with the key π-electron core (π-core) of benzo[de]isoquinolino[1,8-gh]quinolinetetracarboxylic diimide (BQQDI) on the basis of single-crystal OTFT technologies and the band-transport model enabled by two-dimensional molecular packing arrangements. The critical point is the introduction of electronegative nitrogen atoms into the π-core: the nitrogen atoms in BQQDI not only deepen the molecular orbital energies but also allow hydrogen-bonding-like attractive intermolecular interactions to control the aggregated structures, unlike the conventional role of the nitrogen introduced into OSCs only for the former role. Hence, the BQQDI analogues exhibit air-stable OTFT behavior and two-dimensional brickwork packing structures. Specifically, phenethyl-substituted analogue (PhC 2 −BQQDI) has been shown as the first principal BQQDI-based material, demonstrating solution-processable thin-film single crystals, fewer anisotropic transfer integrals, and an effective suppression of molecular motions, leading to band-like electron-transport properties and stress-durable nchannel OTFT performances, in conjunction with the support of computational calculations. Insights into more fundamental points of view have been found by side-chain derivatization and OTFT studies on polycrystalline and single-crystal films. We hope that this Account provides readers with ...

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Section: Design and Synthesis Of Bqqdi For Enhanced 2d Characteristicsmentioning

confidence: 99%

Nitrogen-Containing Perylene Diimides: Molecular Design, Robust Aggregated Structures, and Advances in n-Type Organic Semiconductors

et al. 2022

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“…The ammonia emitted from urea was reacted with TCPF. TCFP emitted CO gas in a weak base, , and the generated CO gas acted as both a reductant and a surface capping agent on the 111 facets of Pd metals, promoting anisotropic 2D growth of Pd nanosheets.…”

Section: Results and Discussionmentioning

confidence: 99%

Facile Synthesis of Pd Nanosheets and Implications for Superior Catalytic Activity

Ando,

Yamamoto,

Kobayashi

et al. 2023

ACS Nano

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As a member of the 2D materials family, 2D metal nanosheets (metallenes) have received increasing attention due to their intriguing properties distinct from those of graphene and other inorganic 2D nanosheets. However, the synthesis of metallenes is still challenging, owing to the lack of an efficient synthetic approach. Here we present a facile one-pot approach to the controlled synthesis of Pd nanosheets. A key feature of this process is a stepwise reaction using 2,4,6-trichlorophenyl formate (TCPF); TCPF emits carbon monoxide gas, which acts as both a reductant and a surface capping agent, promoting the anisotropic 2D growth of the Pd nanosheets. Photoemission spectroscopy revealed some peculiar features of the surface charge and valence band states due to suppressed electron transfer at the 2D surface. This surface state caused improved catalytic activity for the hydrogen evolution reaction compared to that of bulk Pd.

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“…Suzuki–Miyaura coupling with phenylboronic acid and hydrogenation of 22 furnished 3 and 4 , respectively. Condensation of 21 with methanesulfonylchloride afforded 5 , while 6 was obtained from a Pd-catalyzed esterification followed by amidation of 23 with dimethylamine. Derivatives 7 , 9 , and 10 differ with respect to the length of their carbon chain and were synthesized using the corresponding sulfonyl chlorides ( 25a–c ), which were prepared from the corresponding anisole derivatives ( 24a–c ) and treated with amine 21 to provide the corresponding esters ( 26a–c ).…”

Section: Synthetic Chemistry and Eutomer Determinationmentioning

confidence: 99%

Design and Synthesis of Orexin 1 Receptor-Selective Agonists

et al. 2023

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Orexins are a family of neuropeptides that regulate various physiological events, such as sleep/wakefulness as well as emotional and feeding behavior, and that act on two G-protein-coupled receptors, i.e., orexin 1 (OX1R) and orexin 2 receptors (OX2R). Since the discovery that dysfunction of the orexin/OX2R system causes the sleep disorder narcolepsy, several OX2R-selective and OX1/2R dual agonists have been disclosed. However, an OX1R-selective agonist has not yet been reported, despite the importance of the biological function of OX1R. Herein, we report the discovery of a potent OX1R-selective agonist, (R,E)-3-(4-methoxy-3-(N-(8-(2-(3-methoxyphenyl)-N-methylacetamido)-5,6,7,8-tetrahydronaphthalen-2-yl)sulfamoyl)phenyl)-N-(pyridin-4-yl)acrylamide [(R)-YNT-3708; EC50 = 7.48 nM for OX1R; OX2R/OX1R EC50 ratio = 22.5]. The OX1R-selective agonist (R)-YNT-3708 exhibited antinociceptive and reinforcing effects through the activation of OX1R in mice.

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Palladium-Catalyzed External-CO-Free Carbonylation of Aryl Bromides Using 2,4,6-Trichlorophenyl Formate

Cited by 8 publications

References 32 publications

Nitrogen-Containing Perylene Diimides: Molecular Design, Robust Aggregated Structures, and Advances in n-Type Organic Semiconductors

Nitrogen-Containing Perylene Diimides: Molecular Design, Robust Aggregated Structures, and Advances in n-Type Organic Semiconductors

Facile Synthesis of Pd Nanosheets and Implications for Superior Catalytic Activity

Design and Synthesis of Orexin 1 Receptor-Selective Agonists

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