Palladium‐Catalyzed Reductive Carbonylation of Aryl Halides with <i>N</i>‐Formylsaccharin as a CO Source

Ueda, Tsuyoshi; Konishi, Hideyuki; Manabe, Kei

doi:10.1002/anie.201303926

Cited by 216 publications

(110 citation statements)

References 35 publications

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“…DBU was found to be the most effective base, which neutralized the in situ produced HBr during the reaction process to form the ionic liquid [DBUH]Br and simultaneously catalyzed the reaction of CO 2 with PMHS. [39] It is interesting that in the presence of inorganic bases such as Na 2 CO 3 ,C s 2 CO 3 ,a nd NaOH or of organic bases such as NEt 3 and DBN, the desired product was also observed, albeit in low yields (Table1,e ntries [14][15][16][17][18]. This is in contrast to the ineffectiveness of inorganic bases (e.g.,K 2 CO 3 and Cs 2 CO 3 )i nt he Pd/C-catalyzed formylation of iodobenzene with CO 2 and PMHS, [39] implying that Pd(DPPP)Cl 2 has distinct features from those of Pd/C, which will be explored in the following section.…”

Section: Resultsmentioning

confidence: 66%

“…Over the last three decades, palladium-catalyzed CO-free carbonylation reactions have attracted great attention. [9][10][11][12][13][14] For example, Manabe and co-workers [15] adopted Nformylsaccharin as ah ighly reactive CO surrogate and silane as ah ydrogen donor,a nd therebyr ealized reductivec arbonylation of aryl bromides to aryl aldehydes catalyzed by palladium acetate with the aid of al igand and ab ase (Scheme 1a). Subsequently,o ther CO surrogates, including isocyanide [16] and paraformaldehyde, [17] were successfully appliedi nt he carbonylation of aryl/hetaryl iodidesa nd bromides in the presence of different silanes, providing access to aw ide range of aryl/hetaryl aldehydes under relatively mild conditions (Scheme 1b, c).…”

Section: Introductionmentioning

confidence: 98%

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An Efficient and General Method for Formylation of Aryl Bromides with CO₂ and Poly(methylhydrosiloxane)

Yang

Zhao

et al. 2015

Chemistry A European J

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The formylation of aryl halides with CO2 to generate aryl aldehydes is challenging. Herein, we report a novel synthesis of aryl aldehydes by formylation of aryl bromides with CO2 and a waste silane, poly(methylhydrosiloxane) (PMHS). It has been discovered that a simple combination of 1,3-bis(diphenyphosphino)propane (DPPP)-chelated Pd catalyst, Pd(DPPP)Cl2 , with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) is able to effectively catalyze the reaction, leading to aryl aldehydes in moderate to excellent yields, and without any by-products in most cases. Moreover, this route could be extended to the formylation of aryl iodides with high efficiency. This approach is simple, less costly, and environmentally friendly, and also widens the applications of CO2 to form value-added chemicals by the construction of new C-C bonds.

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Section: Resultsmentioning

confidence: 66%

Section: Introductionmentioning

confidence: 98%

An Efficient and General Method for Formylation of Aryl Bromides with CO₂ and Poly(methylhydrosiloxane)

Yang

Zhao

et al. 2015

Chemistry A European J

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“…To our delight, N-formylsaccharin (20k) proved to be effective in this reaction, affording the desired aldehyde in 80% yield (entry 5). 80) 20k was formerly used as a germicide 81) and a formylating agent for amines.…”

Section: Reductive Carbonylationmentioning

confidence: 99%

Creation of Novel Toxic Gas Surrogates and the Development of Safe and Facile Catalytic Reactions

Konishi

2018

Chem. Pharm. Bull.

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The use of toxic gas surrogates in organic reactions instead of the gas itself contributes to enhancing the safety, practicality, and efficiency of the reactions involved. Our efforts toward the creation of toxic gas surrogates and the development of a series of catalytic reactions using these surrogates are described. Improvements in substrate scope during the hydroesterification of alkenes using formates facilitated by the Ru-imidazole catalyst system provided the opportunity to discover that phenyl formate is a useful carbon monoxide (CO) surrogate for the generation of CO and phenol under weakly basic conditions. This discovery triggered the development of highly reactive but stable CO surrogates and a variety of Pd-catalyzed carbonylative transformations. N-Formylsaccharin facilitated the use of additional nucleophiles in carbonylation reactions that provided access to a variety of carbonyl compounds. Detailed experimental and theoretical mechanistic studies into the generation of CO from phenyl formate suggest that CO generation proceeds via a concerted E2 α-elimination. Furthermore, a known surrogate of sulfur dioxide was applied for the first time to the selective syntheses of cyclic sulfonamides and sulfinamides, confirming that the surrogate operates as an "S O" source. Notably, the reactions described herein are scalable and can be performed without the use of external toxic gases and specialized reaction vessels; they are easy and simple to perform and demonstrate enormous potential for industrial application.

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“…Using formylsaccaline and hydrosilanes as the formyl and hydride sources, respectively, the formylation of aryl halides smoothly proceeded in the presence of a Pd catalyst (Scheme 2(b)) 15) .…”

Section: Transformation With Formates: Overviewmentioning

confidence: 99%

Transition-metal Catalyzed Synthesis of Carbonyl Compounds Using Formates or Formamides as Carbonyl Sources

Fujihara

Tsuji

2018

J. Jpn. Petrol. Inst.

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Various available approaches for catalytic carbonylation reactions using formates and formamides with transition metal catalysts are reviewed. Pd complexes catalyze the hydroesterification or hydrocarbamoylation of alkynes using aryl formates or formamides, respectively, as the carbonyl sources. The esterification of aryl halides with aryl formates proceeds in the presence of a Pd catalyst with suitable ligands. Using a Cu complex with a bulky bidentate phosphine ligand is used as a catalyst, boraformylation and silaformylation of allenes efficiently proceeds using alkyl formates as a formyl source.

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Palladium‐Catalyzed Reductive Carbonylation of Aryl Halides with N‐Formylsaccharin as a CO Source

Cited by 216 publications

References 35 publications

An Efficient and General Method for Formylation of Aryl Bromides with CO₂ and Poly(methylhydrosiloxane)

An Efficient and General Method for Formylation of Aryl Bromides with CO₂ and Poly(methylhydrosiloxane)

Creation of Novel Toxic Gas Surrogates and the Development of Safe and Facile Catalytic Reactions

Transition-metal Catalyzed Synthesis of Carbonyl Compounds Using Formates or Formamides as Carbonyl Sources

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Palladium‐Catalyzed Reductive Carbonylation of Aryl Halides with N‐Formylsaccharin as a CO Source

Cited by 216 publications

References 35 publications

An Efficient and General Method for Formylation of Aryl Bromides with CO2 and Poly(methylhydrosiloxane)

An Efficient and General Method for Formylation of Aryl Bromides with CO2 and Poly(methylhydrosiloxane)

Creation of Novel Toxic Gas Surrogates and the Development of Safe and Facile Catalytic Reactions

Transition-metal Catalyzed Synthesis of Carbonyl Compounds Using Formates or Formamides as Carbonyl Sources

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Product

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An Efficient and General Method for Formylation of Aryl Bromides with CO₂ and Poly(methylhydrosiloxane)

An Efficient and General Method for Formylation of Aryl Bromides with CO₂ and Poly(methylhydrosiloxane)