Convenient Palladium‐Catalyzed Reductive Carbonylation of Aryl Bromides Under Gas‐Free Conditions

Ying, Jun; Fu, Lu-Yang; Zhou, Chao; Qi, Xinxin; Peng, Jin‐Bao; Wu, Xiao‐Feng

doi:10.1002/ejoc.201800471

Cited by 9 publications

(5 citation statements)

References 42 publications

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“…4c). Starting from imine 1az (prepared from the corresponding commercially available ketone and methylamine), the benzannulation with PhBBr2 provided the 1,2-azaborine intermediate (3az), which then underwent a Pd-catalyzed formylation 31 and reductive amination to deliver the target BN isostere analogue 7. Compound 7 is stable to air and moisture and can be purified via silica gel chromatography.…”

Section: Resultsmentioning

confidence: 99%

Modular synthesis of 1,2-azaborines via ring-opening BN-isostere benzannulation

Lyu

Tugwell

Chen

et al. 2023

Preprint

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1,2-Azaborines represent a unique class of benzene isosteres that holds great potential for various applications. However, it remains a long-standing challenge to prepare monocyclic 1,2-azaborines in an efficient and modular manner. Here we report a straightforward method to directly access diverse multi-substituted 1,2-azaborines from readily available cyclopropyl imines/ketones and dibromoboranes under relatively mild conditions. The reaction is scalable, shows a broad substrate scope, and tolerates a range of functional groups. The utility of this method is demonstrated in the concise syntheses of BN isosteres of a PD-1/PD-L1 inhibitor and pyrethroid insecticide bifenthrin. Combined experimental and computational mechanistic studies suggest that the reaction pathway involves boron-mediated cyclopropane ring-opening and base-mediated elimination, followed by an unusual low-barrier 6π-electrocyclization accelerated by the BN/CC isomerism.

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Section: Resultsmentioning

confidence: 99%

Modular synthesis of 1,2-azaborines via ring-opening BN-isostere benzannulation

Lyu

Tugwell

Chen

et al. 2023

Preprint

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“…In the second synthesis route of Br-TPD-CHO, formylation of TPD-2Br via bromine–lithium exchange reaction through n -butyllithium also failed. Except the traditional formylation, we also tested palladium-catalyzed reductive carbonylation of aryl and heteroaryl bromides under gas-free conditions by using formic acid and isocyanide as the CO source. , By analyzing the product of the reaction, we only find that the product contained TPD-Br and could not find the aldehyde product by analyzing the NMR of the rest.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of 1-Formyl-3-bromo-thieno[3,4-c]pyrrole-4,6-dione and the Application in A₂–A₁–D–A₁–A₂ Type Non-Fullerene Acceptor

Zhang

et al. 2020

J. Phys. Chem. C

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Nonfullerene acceptors (NFAs) with an A 2 −A 1 −D−A 1 −A 2 skeleton have attracted more and more attention because they can realize high open-circuit voltage (V OC ) and also pair well with the classical p-type polymer of poly(3-hexylthiophene). As a versatile and useful building block, thieno[3,4-c]pyrrole-4,6-dione (TPD) has been widely utilized to construct high-performance ptype photovoltaic polymers but never been used in A 2 −A 1 −D−A 1 −A 2 type NFAs. The main reason is that the critical intermediate of 1-formyl-3-bromo-thieno[3,4-c]pyrrole-4,6-dione (Br-TPD-CHO) cannot be synthesized via traditional methods like Vilsmeier− Haack reaction or bromine−lithium exchange reaction. To solve this problem, here we use Gewald reactions to synthesize the methyl-substituted TPD and then successfully get the intermediate of Br-TPD-CHO by bromination and hydrolysis. Subsequently, a new A 2 −A 1 −D−A 1 −A 2 type NFA was synthesized and named as TPD3, where 2-(1,1-dicyanomethylene)rhodanine (RCN), TPD, and indacenodithiophene (IDT) were used as A 2 , A 1 , and D units, respectively. TPD3 exhibits a highly planar conjugated framework and broad absorption spectrum at 300−720 nm. Preliminary photovoltaic results reveal that TPD3 can realize a high open-circuit voltage (V OC ) of 0.97 V and a moderate power conversion efficiency (PCE) of 7.58% when paired with a benzotriazole-based p-type polymer of J52-Cl. Our results open a unique way to utilize TPD unit for high-performance NFAs.

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“…Melting point 34-37°C. 4-Ethylbenzaldehyde (2h) [7] According to the typical experimental procedure in the experimental part of the paper, the synthesis was carried out at the scale of 2 mmol, and the product was colorless liquid (228.1mg, 85%). 2-Methoxybenzaldehyde (2i) [3] According to the typical experimental procedure in the experimental part of the paper, the synthesis was carried out at the scale of 2 mmol, and the product was pale yellow liquid (193.3mg, 71%).…”

Section: -Chlorobenzaldehyde (2d)mentioning

confidence: 99%

Synthesis of aromatic aldehydes via silver(I)-catalyzed formylation of aryl bromides in DMF promoted by samarium metal in air

Li,

Chen,

et al. 2024

Synthetic Communications

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Convenient Palladium‐Catalyzed Reductive Carbonylation of Aryl Bromides Under Gas‐Free Conditions

Cited by 9 publications

References 42 publications

Modular synthesis of 1,2-azaborines via ring-opening BN-isostere benzannulation

Modular synthesis of 1,2-azaborines via ring-opening BN-isostere benzannulation

Synthesis of 1-Formyl-3-bromo-thieno[3,4-c]pyrrole-4,6-dione and the Application in A₂–A₁–D–A₁–A₂ Type Non-Fullerene Acceptor

Synthesis of aromatic aldehydes via silver(I)-catalyzed formylation of aryl bromides in DMF promoted by samarium metal in air

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Convenient Palladium‐Catalyzed Reductive Carbonylation of Aryl Bromides Under Gas‐Free Conditions

Cited by 9 publications

References 42 publications

Modular synthesis of 1,2-azaborines via ring-opening BN-isostere benzannulation

Modular synthesis of 1,2-azaborines via ring-opening BN-isostere benzannulation

Synthesis of 1-Formyl-3-bromo-thieno[3,4-c]pyrrole-4,6-dione and the Application in A2–A1–D–A1–A2 Type Non-Fullerene Acceptor

Synthesis of aromatic aldehydes via silver(I)-catalyzed formylation of aryl bromides in DMF promoted by samarium metal in air

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Synthesis of 1-Formyl-3-bromo-thieno[3,4-c]pyrrole-4,6-dione and the Application in A₂–A₁–D–A₁–A₂ Type Non-Fullerene Acceptor