Annulative π-extension of indoles and pyrroles with diiodobiaryls by Pd catalysis: rapid synthesis of nitrogen-containing polycyclic aromatic compounds

Kitano, Hiroyuki; Matsuoka, Wataru; Ito, Hideto; Itami, Kenichiro

doi:10.1039/c8sc02802h

Cited by 63 publications

(36 citation statements)

References 71 publications

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“…Thus,t he bottom-up synthesis of PA Hs with atomic precision has attracted considerable attention in molecular engineering and materials sciences.S yntheses of PA Hs have thus far largely relied on multistep methods involving Diels-Alder cycloadditions,c yclotrimerizations,o rc ross-couplings. [2] Recently, catalytic C À Hactivation has emerged as atransformative tool for the rapid construction of extended p-systems,w ith major contributions by the groups of Itami [3] and You, [4] among others. [5] However,t he sustainable nature of this approach is largely compromised by the need for prefunctionalized substrates and/or metal oxidants,s uch as silver(I) salts, which generate stoichiometric amounts of undesired chemical waste.In recent years,t he use of electricity as ar edox agent to power chemical reactions [6] has undergone ar enaissance.…”

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confidence: 99%

Rhodaelectrocatalysis for Annulative C−H Activation: Polycyclic Aromatic Hydrocarbons through Versatile Double Electrocatalysis

et al. 2019

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Rapid access to structurally diversified polycyclic aromatic hydrocarbons (PAHs) in ac ontrolled manner is of key significance in materials sciences.H erein, we describe as trategy featuring two distinct electrocatalytic CÀHt ransformations for the synthesis of novel nonplanar PAHs.T he combination of rhodaelectrooxidative C À Ha ctivation/ [2+ +2+ +2] alkyne annulation of easily accessible boronic acids with electrocatalytic cyclodehydrogenation provided modular access to diversely substituted PAHs with electricity as as ustainable oxidant. The unique molecular topology as well as the photophysical and electronic properties of the thus obtained PAHs were fully analyzed. The unique power of this metallaelectrocatalysis method was demonstrated by the chemoselective assembly of synthetically useful iodo-substituted PAHs.Polycyclic aromatic hydrocarbons (PAHs) have found widespread applications in optoelectronics,bioimaging,and catalysis. [1] Thep hysicochemical properties of PA Hs are determined by their shape, p-extension, and edge topology,which strongly depend on their mode of fabrication. Thus,t he bottom-up synthesis of PA Hs with atomic precision has attracted considerable attention in molecular engineering and materials sciences.S yntheses of PA Hs have thus far largely relied on multistep methods involving Diels-Alder cycloadditions,c yclotrimerizations,o rc ross-couplings. [2] Recently, catalytic C À Hactivation has emerged as atransformative tool for the rapid construction of extended p-systems,w ith major contributions by the groups of Itami [3] and You, [4] among others. [5] However,t he sustainable nature of this approach is largely compromised by the need for prefunctionalized substrates and/or metal oxidants,s uch as silver(I) salts, which generate stoichiometric amounts of undesired chemical waste.In recent years,t he use of electricity as ar edox agent to power chemical reactions [6] has undergone ar enaissance. [7,8] Significant recent impetus was gained by the merger of electrocatalysis with organometallic C À Ha ctivation, thus avoiding the use of toxic and expensive metal oxidants. [9,10] While electrochemical polymerization has been exploited for the synthesis of conducting materials, [11] the bottom-up assembly of atomically precise PA Hm otifs by electrooxidative catalysis has thus far unfortunately proven elusive.I n sharp contrast, we have now devised an ovel strategy for merging two distinct electrocatalytic transformations for the chemoselective assembly of decorated PA Hs.T he development of an unprecedented rhodaelectrocatalyzed [12] C À H activation for the annulative [13] [2+ +2+ +2] cycloaddition of userfriendly boronic acids set the stage for an electro-catalyzed dehydrogenation in ar esource-economical manner (Figure 1). Salient features of our method include 1) rapid, modular access to PA Hs through double electrocatalysis, 2) electricity as as ustainable oxidant, 3) the formation of six new C À Cb onds in ap rogrammable fashion, and 4) outstanding levels of chemoselectivity thr...

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confidence: 99%

Rhodaelectrocatalysis for Annulative C−H Activation: Polycyclic Aromatic Hydrocarbons through Versatile Double Electrocatalysis

et al. 2019

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“…They have also reported a specific study on the palladium-catalyzed annulative π-extension reaction with diiodobiaryls for the preparation of nitrogen-containing PCHs (Scheme 104). 133 The reaction was conducted using 5 mol% of Pd(OPiv)2 associated with 1.5 equivalents of AgOPiv in 7 : 3 mixture of DMF and DMSO at 80 ºC, whereas TfOH was not required anymore.…”

Section: Annulation Through Pd-catalyzed C-h Bond Arylationmentioning

confidence: 99%

“…Palladium-Catalyzed Annulative π-Extension Reaction of N-Methylindole and N-PhenylpyrroleThe authors demonstrated the efficiently of this technology for the construction of unsymmetrical N-PCHs, from simple starting materials. They employed a two-step sequence to synthesize tetrabenzocarbazole (Scheme 105) 133. First, reaction of N-methylpyrrole with 2,2'-diiodo-1,1'-biphenyl was carried out to give the corresponding dibenzo[e,g]indole in 37% yield.…”

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Application of Palladium-Catalyzed C(sp2)–H Bond Arylation to the Synthesis of Polycyclic (Hetero)Aromatics

Hagui

Doucet

2019

Chem

122

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Recently, the use of the palladium-catalyzed inter-and/or intra-molecular C-H bond arylations in the building of various π-extended (hetero)aromatic structures has emerged as a suitable alternative to the previous multi-steps synthesis. Such new methodology even allowed to prepare unprecedented π-extended molecules owing a perfect control of the reaction sites. This review gives an overview of various synthesis of Polycyclic Aromatic Hydrocarbons (PAHs) and PolyCyclic Heteroaromatics (PCHs) with planar, bowl-shaped, and helical structures prepared in high efficiency and selectivity via Pd-catalyzed C-H bond arylations. Bigger Picture Recently, π-extended compounds such as Polycyclic Aromatic Hydrocarbons (PAHs) and PolyCyclic Heteroaromatics (PCHs) have found important applications in the preparation of optoelectronic devices. The degree of π-extension, the topology of the ring fusion, and the periphery of such molecules are essential factors to control their electronic properties at a molecular level. The traditional approach to prepare nanographenes and heteroatom-doped nanographenes relies on Scholl reaction. However, such methodology suffers from limitations such as functional group compatibility. Catalysis plays a pivotal role in the discovery of new transformations enabling the synthesis of novel molecules, including organic materials. Among various catalytic transformations, Pd-catalyzed C-H bond arylation has emerged as an important tool for the construction of well-decorated polycyclic (hetero)aromatic molecules. Such direct approaches have a considerable impact on the synthesis of PAHs and PCHs by shortening the synthetic scheme and also providing a momentous opportunity to design novel structures. eTOC Blurb: This review highlights the potential of Pd-catalyzed C-H bond arylation for the synthesis of π-extended compounds that include

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“…The detailed synthetic routes of Cz-TD and TBC-TD are shown in Scheme S1, Supporting Information. First, the key intermediate TBC-TeBr was synthesized by two simple reactions of the commercially available compounds, [39][40][41] and the target molecules were readily obtained by the classical Buchwald-Hartwig C-N coupling reaction of the tetrabromide-substituted TBC or Cz and DPA group. These two HTMs were fully characterized by nuclear magnetic resonance (NMR) spectroscopy, highresolution mass spectroscopy (HRMS), and elemental analysis (EA) (Figure S1-S9, Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

Hole‐Transporting Molecules with Tetrabenzo[a,c,g,i]carbazole Core for Highly Efficient Perovskite Solar Cells

Liu

Ling

et al. 2021

Solar RRL

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Hole‐transporting materials (HTMs) are the key component of perovskite solar cells (PSCs) for the role of extracting photogenerated holes, as well as the charge transporting between perovskite layer and metal electrode. Herein, with the aim to enhance the hole mobility by compact molecular packing, the modification of HTMs focuses on the extension of conjugated cores from the commonly used carbazole (Cz) to tetrabenzo[a,c,g,i]carbazole (TBC). Because of the closely cofacial stacking mode of the TBC core with an X‐type symmetric structure, the resultant TBC‐2,7,11,16‐tetra‐diphenylamine (TD) can achieve a hole mobility of 6.6 × 10−4 cm2 V−1 s−1 and the corresponding conversion efficiency of 20.52%, higher than that of the analogue Cz‐TD (18.34%).

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Annulative π-extension of indoles and pyrroles with diiodobiaryls by Pd catalysis: rapid synthesis of nitrogen-containing polycyclic aromatic compounds

Abstract: A palladium-catalyzed one-step annulative π-extension (APEX) reaction of indoles and pyrroles that allows rapid access to nitrogen-containing polycyclic aromatic compounds is described.

Cited by 63 publications

References 71 publications

Rhodaelectrocatalysis for Annulative C−H Activation: Polycyclic Aromatic Hydrocarbons through Versatile Double Electrocatalysis

Rhodaelectrocatalysis for Annulative C−H Activation: Polycyclic Aromatic Hydrocarbons through Versatile Double Electrocatalysis

Application of Palladium-Catalyzed C(sp2)–H Bond Arylation to the Synthesis of Polycyclic (Hetero)Aromatics

Hole‐Transporting Molecules with Tetrabenzo[a,c,g,i]carbazole Core for Highly Efficient Perovskite Solar Cells

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