Intermediate formation enabled regioselective access to amide in the Pd-catalyzed reductive aminocarbonylation of olefin with nitroarene

Li, Yang; Shi, Lijun; Xia, Chungu; Li, Fuwei

doi:10.1016/s1872-2067(20)63561-6

Cited by 14 publications

(7 citation statements)

References 58 publications

(90 reference statements)

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“…As shown in Scheme 1C, we hypothesized that amide is possibly beneficial to initiating the aminopalladation of alkene and retarding the side oxidative carbonylation to urea, then delivering to the desired aminocarbonylation to establish alkene difunctionalization and cyclization to produce seven‐membered diazepanone. Continuing our interest in the carbonylation reactions to synthesize heterocycles, [ 10 ] herein, we report an efficient PdCl 2 ‐ catalyzed tandem oxidative carbonylation reactions of amine‐ tethered alkenylamides without the addition of external Cl − resource to access 1,4‐diazepanone derivatives in good to excellent yields. Systematic control experiments suggest that a seven‐ membered N ‐heterocyclic Pd complex is the key intermediate, which is different from the reported aza‐Wacker cyclization‐carbonylation, wherein an acyl metal species is claimed to be the important intermediate.…”

Section: Background and Originality Contentmentioning

confidence: 99%

Palladium‐Catalyzed Tandem Carbonylative Aza‐Wacker‐Type Cyclization of Nucleophile Tethered Alkene to Access Fused N‐Heterocycles

Shi

Wen

2020

Chin. J. Chem.

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Main observation and conclusion Although tandem reactions offer rapid access to structurally complex molecules in one‐pot reaction, the selectivity issue needs to be addressed particularly when incompatible step reactions are involved. Herein, we report the selective synthesis of fused N‐heterocycles from nucleophile‐tethered alkenylamide and carbon monoxide via palladium (Pd)‐catalyzed tandem carbonylative aza‐Wacker‐type cyclization. The electron‐deficient nature of amide N—H and the intramolecular coordination of Pd with alkene accelerate the aminopalladation and effectively prevent the side oxidative carbonylation of diamine moiety to form urea. It is also found that the reported acyl Pd chloride intermediate may not be involved in this tandem cyclization. This work not only provides an efficient synthetic route to fused 1,4‐diazepanones and 1,4‐diazepanes but also inspires further development of tandem reactions for the diverse synthesis of heterocycles.

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Section: Background and Originality Contentmentioning

confidence: 99%

Palladium‐Catalyzed Tandem Carbonylative Aza‐Wacker‐Type Cyclization of Nucleophile Tethered Alkene to Access Fused N‐Heterocycles

Shi

Wen

2020

Chin. J. Chem.

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“…On the basis of the above results and the previous reports, , the mechanism of carbonylation of aryl iodides with amine over Pd catalyst containing different phosphines was proposed in Scheme . Initially, mixing of PdCl 2 (MeCN) 2 with the diphosphine ligand in CO atmosphere leads to the formation of an active Pd(0)-intermediate ( A ).…”

Section: Resultsmentioning

confidence: 68%

Pd-Catalyst Containing a Hemilabile P,C-Hybrid Ligand in Amino Dicarbonylation of Aryl Halides for Synthesis of α-Ketoamides

et al. 2021

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The amino dicarbonylation of aryl halides affording α-ketoamides with Pd catalysts is highly dependent on the stereoelectronic properties of the involved ligands. Ionic diphosphine ligand L4 can serve as precursor of a hemilabile P,C (phosphine, carbene)-hybrid ligand to form a stable Pd(II)complex, Pd-L4. In contrast, analogues L1−L3 with a similar 1-(thiophen-3-yl)-benzimidazolyl skeleton behave as typical (mono/ di)phosphines. The catalytic system resulting from the complexation of PdCl 2 (MeCN) 2 and L4 exhibits good catalytic performance in terms of aryl iodides conversion (81−95%) and αketoamide selectivity (80−91%), as well as the available recyclability in the RTIL of [Bpy]BF 4 . The in situ FT-IR analysis reveals that the PdCl 2 (MeCN) 2 −L4 catalytic system favors the amino dicarbonylation toward α-ketoamides according to the proposed mechanism of cycle I, which involves two independent COinsertion steps.

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“…Xia and Li and co-workers also reported regioselective formation of amides 10 or 11 via amino carbonylation of olefins 9 with nitroarenes 1 under the influence of Pd-catalyst, wherein, CO acted as reductant as well as the carbonyl source (Scheme 5). [17] It was found that regioselectivity and chemoselectivity of reaction was affected by the counter anion of Pdcatalyst precursors. The authors discovered that whereas use of K 2 PdCl 4 produced the branched amide 10, use of Pd(Me-(CN) 4 (OTf) 2 gave the linear amide 11 exclusively.…”

Section: Aminocarbonylation With Alkenes and Alkynesmentioning

confidence: 99%

Direct Access to Amides from Nitro‐Compounds via Aminocarbonylation and Amidation Reactions: A Minireview

Barak

Batra

2021

The Chemical Record

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The ubiquity of the amide bond in functional molecules including proteins, natural products, pharmaceuticals, agrochemicals and materials provides impetus to design and develop newer strategies for the generation of this linkage. Owing to growing awareness about sustainability and development of benign strategies, the traditional route of synthesis of amides via reaction between carboxylic acids and amines in the presence of stoichiometric amount of coupling reagents is tagged to be harsh and wasteful. In one of the unconventional routes, nitro compounds are used directly as amine surrogates for preparing amides mostly via aminocarbonylation and amidation reactions. Typically, such processes involves nitroarenes owing to their propensity to transform into nitroso, hydroxylamine, diazo, hydrazine or aniline intermediates in situ under the influence of suitable catalyst or oxidant. This short review provides the comprehensive overview of these reactions including insight into the scope and their mechanisms.

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Intermediate formation enabled regioselective access to amide in the Pd-catalyzed reductive aminocarbonylation of olefin with nitroarene

Cited by 14 publications

References 58 publications

Palladium‐Catalyzed Tandem Carbonylative Aza‐Wacker‐Type Cyclization of Nucleophile Tethered Alkene to Access Fused N‐Heterocycles

Palladium‐Catalyzed Tandem Carbonylative Aza‐Wacker‐Type Cyclization of Nucleophile Tethered Alkene to Access Fused N‐Heterocycles

Pd-Catalyst Containing a Hemilabile P,C-Hybrid Ligand in Amino Dicarbonylation of Aryl Halides for Synthesis of α-Ketoamides

Direct Access to Amides from Nitro‐Compounds via Aminocarbonylation and Amidation Reactions: A Minireview

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