Novel palladium-catalyzed carbonylation of organic halides by chloroform and alkali

Grushin, Vladimir V.; Alper, Howard

doi:10.1021/om00034a016

Cited by 128 publications

(113 citation statements)

References 0 publications

Supporting

Mentioning

107

Contrasting

Unclassified

Order By: Relevance

“…At the time of this important discovery of CO generation from 20a, various CO surrogates were known, including formic acid, [48][49][50] paraformaldehyde, 50) N,N-dimethylformamide (DMF), 51) chloroform, 52) aldehydes, [53][54][55][56] metal carbonyl complexes, 57) acid chlorides, 58) and silacarboxylic acids. 59) Alkyl formates 60) had been also reported to act as CO surrogates.…”

Section: Discovery Of Phenyl Formate As a Co Surrogatementioning

confidence: 99%

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

Konishi

2018

CHEMICAL & PHARMACEUTICAL BULLETIN

View full text Add to dashboard Cite

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.

show abstract

Section: Discovery Of Phenyl Formate As a Co Surrogatementioning

confidence: 99%

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

Konishi

2018

CHEMICAL & PHARMACEUTICAL BULLETIN

View full text Add to dashboard Cite

show abstract

“…Darauf aufbauend entwickelten Alper und Grushin eine Palladium-katalysierte Hydroxycarbonylierung von Arylhalogeniden mit Chloroform in wässriger alkalischer Lösung (Schema 16). [22] Auch Alkenyl-und Benzylhalogenide werden unter diesen Bedingungen zu den entsprechenden Carbonsäuren umgesetzt.…”

Section: Chloroformunclassified

“…Pd-katalysierte Hydroxycarbonylierung mit Chloroform/ KOH. [22] Schema 17. Rh-katalysierte Pauson-Khand-Reaktion mit dem Aldehyd 4. phosphanyl)-1,1'-binaphthyl) als chiralem Phosphanliganden zu einer asymmetrischen Variante weiterentwickelt (Schema 20).…”

Section: Aldehydeunclassified

Katalytische Carbonylierungen: kein Bedarf an Kohlenmonoxid

2004

View full text Add to dashboard Cite

Erste bahnbrechende Erfolge in der metallorganischen Katalyse gelangen mit der Entdeckung der Roelen‐Reaktion 1938 (Hydroformylierung mit Kohlenmonoxid und Wasserstoff) und der Reppe‐Reaktion 1939 (Hydrocarboxylierung mit Kohlenmonoxid und Wasser). Seither haben Carbonylierungen mit Kohlenmonoxid einen festen Platz in der metallorganischen Chemie und der organischen Synthese. Allerdings ist die Verwendung von gasförmigem Kohlenmonoxid problematisch (toxisches Treibhausgas), sodass in neuerer Zeit Strategien zur Verwendung anderer Carbonylierungsreagentien entwickelt wurden. Dieser Kurzaufsatz beschreibt Carbonylierungen, die ohne direkten Einsatz von Kohlenmonoxid durchgeführt werden können.

show abstract

“…The most plausible pathway for the formation of 6 is by attack of OH À on the iodo-analogue of 2 with concomitant formation of Pd 0 and a proton; such generation of Pd 0 and phosphine oxide from Pd IIphosphine complexes during catalytic transformations of aryl halides is well documented. [37,38] A less likely and more speculative path involves reaction of OH À with PtCl 2 (dmapm), generated by equilibrium (2), to give an intermediate such as ∫Pt(dmapmO)∫ which is transformed in a subsequent step(s) to give 6 (e.g., by double oxidative addition of PhI followed by reductive elimination of biphenyl). Of note, even under the high temperature, strong base conditions of the reaction, a significant proportion of the catalyst survived intact (based on the composition of the isolated crystals).…”

Section: Oxidative Degradationmentioning

confidence: 99%

Homo- and Heterobimetallic Precursor Catalysts for the Heck Reaction, and a Proposal for a General Catalytic Cooperativity Index

Jones

James

2002

Advanced Synthesis & Catalysis

View full text Add to dashboard Cite

Homo‐ (Pd2) and heterobimetallic (PtPd) complexes supported by a P,P‐bridging, bis(P,N‐chelating) coordination mode of the potentially hexadentate ligand 1,1‐bis[di(o‐N,N‐dimethylanilinyl)phosphino]methane (dmapm) are effective catalyst precursors for the aerobic Heck coupling of iodobenzene and styrene at 100 °C in DMF/H2O solution containing K2CO3. This medium allows for trivial separation of the trans‐stilbene product which precipitates after the reaction mixture is cooled. The bimetallic precursors are more active than predicted from the sum of the activities of complexes chosen to mimic their mono‐metallic “half units,” suggesting some degree of intermetallic cooperativity during the reaction. A non‐linear dependence of initial rate on catalyst concentration implies, however, that the complexes do not remain intact, and may be involved in dissociative equilibria with non‐dmapm containing monometallic components that are more active species for the Heck coupling. The complexes are slowly degraded by oxidation at a phosphorus centre. A general index for quantifying the degree of intermetallic cooperativity during a catalytic cycle is proposed and its utility and limitations are discussed.

show abstract

Novel palladium-catalyzed carbonylation of organic halides by chloroform and alkali

Cited by 128 publications

References 0 publications

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

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

Katalytische Carbonylierungen: kein Bedarf an Kohlenmonoxid

Homo- and Heterobimetallic Precursor Catalysts for the Heck Reaction, and a Proposal for a General Catalytic Cooperativity Index

Contact Info

Product

Resources

About