Synthesis of 1,4-keto esters and 1,4-diketones via palladium-catalyzed acylation of siloxycyclopropanes. Synthetic and mechanistic studies

1991 ◽  
Vol 56 (8) ◽  
pp. 2809-2821 ◽  
Author(s):  
Tsutomu Fujimura ◽  
Satoshi Aoki ◽  
Eiichi Nakamura
Keyword(s):  
Mechanistic Studies ◽  
Keto Esters ◽  
Palladium Catalyzed

Mechanistic studies on palladium-catalyzed double carbonylation of aryl iodides affording α-keto esters

1988 ◽  
Vol 48 (1) ◽  
pp. 69-79 ◽  
Author(s):  
Hiroshi Yamashita ◽  
Toshiyasu Sakakura ◽  
Toshi-Aki Kobayashi ◽  
Masato Tanaka
Keyword(s):  
Mechanistic Studies ◽  
Keto Esters ◽  
Aryl Iodides ◽  
Palladium Catalyzed

scholarly journals Palladium-catalyzed alkylation of unactivated olefins

2004 ◽  
Vol 76 (3) ◽  
pp. 671-678 ◽  
Author(s):  
Ross A. Widenhoefer
Keyword(s):  
Good Yield ◽  
Catalytic Amount ◽  
Outer Sphere ◽  
Deuterium Labeling ◽  
Carbon Nucleophiles ◽  
Keto Esters ◽  
Reactive Carbon ◽  
Aryl Ketones ◽  
Palladium Catalyzed ◽  
Hydride Elimination

The reaction of a 3-butenyl β-diketone with a catalytic amount of PdCl2(CH3CN)2 in dioxane at room temperature led to olefin hydroalkylation and formation of the corresponding 2-acylcyclohexanone in good yield as a single regioisomer. Deuterium-labeling experiments for the hydroalkylation of 7-octene-2,4-dione were in accord with a mechanism involving outer-sphere attack of the pendant enol on a palladium-complexed olefin to form a palladium cyclohexyl species, followed by palladium migration via iterative β-hydride elimination/addition and protonolysis from a palladium enolate complex. In comparison to a 3-butenyl β-diketone, reaction of a 4-pentenyl β-diketone with a catalytic amount of PdCl2(CH3CN)2 in the presence of CuCl2 led to oxidative alkylation and formation of the corresponding 2-acyl-3-methyl-2-cyclohexenone in good yield as a single isomer. Unactivated olefins tethered to less reactive carbon nucleophiles such as β-keto esters, α-aryl ketones, and even dialkyl ketones underwent palladium-catalyzed hydroalkylation in the presence of Me3SiCl or HCl to form the corresponding cyclohexanones in moderate-to-good yield with high regioselectivity.

scholarly journals A rational pre-catalyst design for bis-phosphine mono-oxide palladium catalyzed reactions

2017 ◽  
Vol 8 (4) ◽  
pp. 2841-2851 ◽  
Author(s):  
Yining Ji ◽  
Hongming Li ◽  
Alan M. Hyde ◽  
Qinghao Chen ◽  
Kevin M. Belyk ◽  
...  
Keyword(s):  
Rational Design ◽  
Catalyst Design ◽  
Mechanistic Studies ◽  
Catalyst Activation ◽  
Palladium Catalyzed ◽  
Catalyzed Reactions

Detailed mechanistic studies of a Pd-catalyzed asymmetric C–N coupling led to a rational design of a new series of bis-phosphine mono-oxides ligated Pd(ii) pre-catalysts that allow for reliable and complete catalyst activation.

I2/TBHP-Promoted Approach to α-Keto Esters from Trifluoromethyl β-Diketones and Alcohols via C–C Bond Cleavage

Synlett ◽  
2017 ◽  
Vol 28 (15) ◽  
pp. 2018-2023 ◽  
Author(s):  
Xiang Fang ◽  
Xueyan Yang ◽  
Tongle Shao ◽  
Jun Zhou ◽  
Chen Jin ◽  
...  
Keyword(s):  
Oxidative Coupling ◽  
Bond Cleavage ◽  
Bond Formation ◽  
Coupling Reaction ◽  
Mechanistic Studies ◽  
Metal Free ◽  
Oxidation Pathway ◽  
Keto Esters ◽  
Oxidative Coupling Reaction

A metal-free oxidative coupling reaction of trifluoromethyl β-diketones with alcohols for the synthesis of α-keto esters in good to excellent yields has been developed. Preliminary mechanistic studies suggest that an I2/TBHP promoted sequential iodination, C–C bond cleavage, C–O bond formation and oxidation pathway is involved in this reaction.

scholarly journals Mechanistic Studies of the Palladium-Catalyzed Desulfinative Cross-Coupling of Aryl Bromides and (Hetero)Aryl Sulfinate Salts

2020 ◽  
Vol 142 (7) ◽  
pp. 3564-3576 ◽  
Author(s):  
Antoine de Gombert ◽  
Alasdair I. McKay ◽  
Christopher J. Davis ◽  
Katherine M. Wheelhouse ◽  
Michael C. Willis
Keyword(s):  
Cross Coupling ◽  
Mechanistic Studies ◽  
Aryl Bromides ◽  
Palladium Catalyzed

scholarly journals Palladium-catalyzed Suzuki-Miyaura coupling of thioureas or thioamides

2019 ◽  
Vol 10 (1) ◽  
Author(s):  
Shaoyu Mai ◽  
Wendong Li ◽  
Xue Li ◽  
Yingwei Zhao ◽  
Qiuling Song
Keyword(s):  
Silver Salt ◽  
Coupling Reaction ◽  
Coupling Reactions ◽  
Mechanistic Studies ◽  
Aromatic Rings ◽  
Cross Coupling Reactions ◽  
Broad Array ◽  
Palladium Catalyzed

AbstractCross-coupling reactions involving metal carbene intermediates play an increasingly important role in C–C bond formation. Expanding the carbene precursors to a broader range of starting materials and more diverse products is an ongoing challenge in synthetic organic chemistry. Herein, we report a Suzuki-Miyaura coupling reaction of in situ-generated Pd–carbene complexes via desulfurization of thioureas or thioamides. This strategy enables the preparation of a broad array of substituted amidinium salts and unsymmetrical diaryl ketones. The reaction is readily scalable, compatible with bromo groups on aromatic rings, tolerant to moisture and air and has a broad substrate scope. Furthermore, a single crystal structure of Pd-diaminocarbene complex is obtained and proven to be the key intermediate in both catalytic and stoichiometric reactions. Preliminary mechanistic studies demonstrate the dual role of the silver salt as a desulfurating reagent assisting the elimination of sulfur and as oxidant facilitating the PdII/Pd0/PdII catalytic cycle.

Palladium Catalyzed Heck Reaction of Arenediazonium Tetrafluoroborate Salts with Baylis—Hillman Adducts: Production of α-Benzyl-β-keto Esters.

ChemInform ◽  
2006 ◽  
Vol 37 (22) ◽  
Author(s):  
Rolando Perez ◽  
Demetrius Veronese ◽  
Fernando Coelho ◽  
O. A. C. Antunes
Keyword(s):  
Heck Reaction ◽  
Keto Esters ◽  
Palladium Catalyzed
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