A Practical Strategy for the Structural Diversification of Aliphatic Scaffolds through the Palladium-Catalyzed Picolinamide-Directed Remote Functionalization of Unactivated C(sp3)H Bonds

2011 ◽  
Vol 123 (22) ◽  
pp. 5298-5302 ◽  
Author(s):  
Gang He ◽  
Gong Chen
Keyword(s):  
Practical Strategy ◽  
Palladium Catalyzed ◽  
Structural Diversification

Palladium Catalyzed Stereospecific Arylation of Biocatalytically Derived Cyclic 1,3-Dienes: Chirality Transfer via a Heck-Type Mechanism

2019 ◽  
Author(s):  
Andrew J. Paterson ◽  
Petter Dunås ◽  
Martin Rahm ◽  
Per-Ola Norrby ◽  
Gabriele Kociok-Kohn ◽  
...  
Keyword(s):  
Benzoic Acid ◽  
Ralstonia Eutropha ◽  
Three Dimensional ◽  
Dimensional Structure ◽  
Chirality Transfer ◽  
Weinreb Amide ◽  
Stereogenic Centers ◽  
Palladium Catalyzed ◽  
Tricyclic Ketone ◽  
Structural Diversification

Microbial arene oxidation of benzoic acid with Ralstonia eutropha B9 provides a chiral highly functionalized cyclohexadiene, suitable for further structural diversification. Subjecting this scaffold to a palladium-catalyzed Heck reaction effects a regioselective and stereospecific arylation of the cyclohexadiene ring, with transfer of the stereogenic information installed in the microbial arene oxidation. Functional groups that were well tolerated on the diene substrate included a range of esters, amides and a Weinreb amide, affording a total of 23 different products in good yields. These products, which can be considered as latent enolic nucleophiles, also possess a unique three dimensional structure which can be utilized in further stereoselective transformations. This was demonstrated by subjecting one of the products, which contained a protected aldehyde, to a tandem deprotection – cyclization sequence. The reaction proceeded with complete stereoselectivity and afforded a tricyclic ketone product possessing four stereogenic centers. This demonstrates the capability of the method to introduce stereochemical complexity from non-chiral benzoic acid in just a few steps. Quantum chemical calculations have provided insight into the mechanism of the palladium-catalyzed arylation. The high selectivity can be explained both by a kinetic preference for the observed arylation position and by reversible carbopalladation in competing positions.<br><br>

Selective palladium-catalyzed carbonylative synthesis of aurones with formic acid as the CO source

RSC Advances ◽  
2016 ◽  
Vol 6 (67) ◽  
pp. 62810-62813 ◽  
Author(s):  
Xinxin Qi ◽  
Rui Li ◽  
Xiao-Feng Wu
Keyword(s):  
Formic Acid ◽  
Practical Strategy ◽  
Palladium Catalyzed

A general and practical strategy has been developed to prepare aurone derivatives.

Efficient, versatile and practical palladium-catalyzed highly regioselective ortho-halogenation of azoxybenzenes

2016 ◽  
Vol 14 (1) ◽  
pp. 323-329 ◽  
Author(s):  
Meng Sun ◽  
Xiangxiang Chen ◽  
Liang Zhang ◽  
Wei Sun ◽  
Zhe Wang ◽  
...  
Keyword(s):  
Palladium Catalysts ◽  
Highly Efficient ◽  
Practical Strategy ◽  
Palladium Catalyzed

A highly efficient and practical strategy of regio-selective ortho-halogenation of azoxybenzenes with NXS in the presence of palladium catalysts has been developed in good to excellent yields.

scholarly journals Developing backbone-modified Mor-DalPhos ligand variants for use in palladium-catalyzed C–N and C–C cross-coupling

2018 ◽  
Vol 96 (7) ◽  
pp. 712-721 ◽  
Author(s):  
Mark A. MacLean ◽  
Craig A. Wheaton ◽  
Mark Stradiotto
Keyword(s):  
Solid State ◽  
Coordination Mode ◽  
Cross Coupling ◽  
Catalytic Efficiency ◽  
Significant Degree ◽  
Present Contribution ◽  
Bite Angle ◽  
Solution Studies ◽  
Palladium Catalyzed ◽  
Structural Diversification

The present contribution describes the systematic structural diversification of the κ2-P,N DalPhos ligand family in an effort to improve catalytic efficiency in the monoarylation of ammonia and acetone. The study is focused primarily on modifying the backbone phenylene linker, while retaining the same bite angle and steric bulk as the Mor-DalPhos ligand through the use of P(1-Ad)2 and morpholine donors. Eight new variants of Mor-DalPhos were prepared; two of these feature a pyridine linker (L1, L2), and five others feature either electron-donating (L3, L4) or electron-withdrawing (L5–L7) substituents on the phenylene linker. Additionally, thiomorpholino substitution (L8) was performed to investigate the effects of a possible tridentate coordination mode. Precatalyst complexes of the general formula LPd(cinnamyl)Cl were prepared and characterized in both solution and solid state. Solution studies demonstrated a significant degree of lability in the Pd–N bond, whereby dynamic behavior is seen to be dependent on the nature of the ligand backbone. The utility of these new ligands in the palladium-catalyzed monoarylation of ammonia or acetone was then surveyed. Notably, pyridine-derived ligand variants (L1, L2) were observed to out-perform parent Mor-DalPhos in the latter transformations.

Synthesis of S-aryl thioesters via palladium-catalyzed thiocarbonylation of aryl iodides and aryl sulfonyl hydrazides

2020 ◽  
Vol 7 (19) ◽  
pp. 2938-2943
Author(s):  
Yeojin Kim ◽  
Kwang Ho Song ◽  
Sunwoo Lee
Keyword(s):  
Aryl Iodide ◽  
Aryl Iodides ◽  
Palladium Catalyzed

Aryl sulfonyl hydrazide reacted with aryl iodide in the presence of CO to give the corresponding S-aryl thioesters.

Palladium-catalyzed carbonylative transformation of aryl iodides and sulfonyl chlorides: convenient access to thioesters

2020 ◽  
Vol 7 (6) ◽  
pp. 885-889 ◽  
Author(s):  
Xinxin Qi ◽  
Zhi-Peng Bao ◽  
Xiao-Feng Wu
Keyword(s):  
Sulfonyl Chlorides ◽  
Aryl Iodides ◽  
Palladium Catalyzed ◽  
Convenient Access

A palladium-catalyzed carbonylative transformation of aryl iodides and sulfonyl chlorides to thioesters has been studied.

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