Mechanistic Studies of a Palladium-Catalyzed Intramolecular Hydroamination of Unactivated Alkenes:  Protonolysis of a Stable Palladium Alkyl Complex Is the Turnover-Limiting Step

2008 ◽  
Vol 130 (9) ◽  
pp. 2786-2792 ◽  
Author(s):  
Brian M. Cochran ◽  
Forrest E. Michael
Keyword(s):  
Mechanistic Studies ◽  
Limiting Step ◽  
Palladium Catalyzed

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.

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.

scholarly journals Palladium-catalyzed α-arylation for the addition of small rings to aromatic compounds

2019 ◽  
Vol 10 (1) ◽  
Author(s):  
Zhi-Tao He ◽  
John F. Hartwig
Keyword(s):  
Electronic Properties ◽  
Aromatic Compounds ◽  
Ring Opening ◽  
Biologically Active ◽  
High Yield ◽  
Protecting Group ◽  
Mechanistic Studies ◽  
Claisen Condensation ◽  
Wide Range ◽  
Palladium Catalyzed

Abstract Small, strained rings have rigid, defined conformations and unique electronic properties. For these reasons, many groups seek to use these subunits to form biologically active molecules. We report a generally applicable approach to attach small rings to a wide range of aromatic compounds by palladium-catalyzed α-arylation of cyclopropyl, cyclobutyl and azetidinyl esters. The direct α-arylation of cyclopropyl esters and cyclobutyl esters is achieved in high yield by ensuring that the rate of coupling exceeds the rate of Claisen condensation. The α-arylation of azetidines is achieved without ring opening of the strained saturated heterocycle by conducting the reactions with an azetidine derivative bearing a benzyl protecting group on nitrogen. Mechanistic studies show that the α-arylation of small rings is challenging because of the weak acidity of α C-H bond (cyclopropanes), strong sensitivity of the strained esters to Claisen condensation (cyclobutatanes), or facile decomposition of the enolates (azetidinyl esters).

scholarly journals Pd-catalyzed intramolecular addition of active methylene compounds to alkynes with subsequent cross-coupling with (hetero)aryl halides

RSC Advances ◽  
2019 ◽  
Vol 9 (68) ◽  
pp. 40152-40167 ◽  
Author(s):  
Aleksandra Błocka ◽  
Paweł Woźnicki ◽  
Marek Stankevič ◽  
Wojciech Chaładaj
Keyword(s):  
Functional Group ◽  
Cross Coupling ◽  
Aryl Halides ◽  
Mechanistic Studies ◽  
Rate Limiting Step ◽  
Limiting Step ◽  
Active Methylene Compounds ◽  
Tandem Cyclization ◽  
Rate Limiting ◽  
Active Methylene

A tandem cyclization/coupling of acetylenic active methylene compounds with aryl halides features broad scope and excellent functional group compatibility. Mechanistic studies identified 5-exo-dig cyclization as the rate limiting step.

scholarly journals Palladium-Catalyzed Intra- and Intermolecular C–H Arylation Using Mesylates: Synthetic Scope and Mechanistic Studies

ACS Catalysis ◽  
2014 ◽  
Vol 4 (7) ◽  
pp. 2395-2401 ◽  
Author(s):  
Devin M. Ferguson ◽  
Stacey R. Rudolph ◽  
Dipannita Kalyani
Keyword(s):  
Mechanistic Studies ◽  
Palladium Catalyzed

Palladium-Catalyzed Deformylation Reactions with Detailed Experimental and in Silico Mechanistic Studies

2017 ◽  
Vol 2017 (28) ◽  
pp. 4168-4174 ◽  
Author(s):  
Atanu Modak ◽  
Sujoy Rana ◽  
Ashwini K. Phukan ◽  
Debabrata Maiti
Keyword(s):  
In Silico ◽  
Mechanistic Studies ◽  
Palladium Catalyzed

scholarly journals Palladium-catalyzed Heck-type reaction of secondary trifluoromethylated alkyl bromides

2017 ◽  
Vol 13 ◽  
pp. 2610-2616 ◽  
Author(s):  
Tao Fan ◽  
Wei-Dong Meng ◽  
Xingang Zhang
Keyword(s):  
Alkyl Radical ◽  
Functional Group ◽  
High Efficiency ◽  
Mechanistic Studies ◽  
Reaction Conditions ◽  
Type Reaction ◽  
Alkyl Bromides ◽  
Reaction Proceeds ◽  
Palladium Catalyzed ◽  
Hydroxy Groups

An efficient palladium-catalyzed Heck-type reaction of secondary trifluoromethylated alkyl bromides has been developed. The reaction proceeds under mild reaction conditions with high efficiency and excellent functional group tolerance, even towards formyl and hydroxy groups. Preliminary mechanistic studies reveal that a secondary trifluoromethylated alkyl radical is involved in the reaction.

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