Solution Photochemistry and Kinetics of Palladium(II) Complexes

Cooper, J. B.; Venezky, David L.; Lorenz, Timothy

doi:10.1007/978-1-4613-2958-9_56

Cited by 3 publications

(3 citation statements)

References 14 publications

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“…We envisioned that photoirradiation of a Pd(0) complex may facilitate a single-electron-transfer process to activate alkyl halides (Figure b). The use of irradiation with a xenon lamp to facilitate radical-type oxidative addition has been reported by Ryu et al In addition, Pd(II) complexes can undergo geometric exchange from square planar to tetrahedron under irradiation . This geometric change is caused by the formation of an excited-state Pd(II) complex involving outer orbitals that possess higher energy and may induce radical reactivity of the alkyl-Pd(II) species (Figure c) .…”

Section: Introductionmentioning

confidence: 99%

“…The use of irradiation with a xenon lamp to facilitate radical-type oxidative addition has been reported by Ryu et al 14 In addition, Pd(II) complexes can undergo geometric exchange from square planar to tetrahedron under irradiation. 15 This geometric change is caused by the formation of an excited-state Pd(II) complex involving outer orbitals that possess higher energy and may induce radical reactivity of the alkyl-Pd(II) species (Figure 1c). 16 This photoexcitation effect may suppress undesired β-H elimination by preventing bonding of the alkyl radical to palladium, especially for tertiary alkyl radicals with large steric bulkiness.…”

Section: Introductionmentioning

confidence: 99%

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Irradiation-Induced Heck Reaction of Unactivated Alkyl Halides at Room Temperature

et al. 2017

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The palladium-catalyzed Mizoroki-Heck reaction is arguably one of the most significant carbon-carbon bond-construction reactions to be discovered in the last 50 years, with a tremendous number of applications in the production of chemicals. This Nobel-Prize-winning transformation has yet to overcome the obstacle of its general application in a range of alkyl electrophiles, especially tertiary alkyl halides that possess eliminable β-hydrogen atoms. Whereas most palladium-catalyzed cross-coupling reactions utilize the ground-state reactivity of palladium complexes under thermal conditions and generally apply a single ligand system, we report that the palladium-catalyzed Heck reaction proceeds smoothly at room temperature with a variety of tertiary, secondary, and primary alkyl bromides upon irradiation with blue light-emitting diodes in the presence of a dual phosphine ligand system. We rationalize that this unprecedented transformation is achieved by utilizing the photoexcited-state reactivity of the palladium complex to enhance oxidative addition and suppress undesired β-hydride elimination.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Irradiation-Induced Heck Reaction of Unactivated Alkyl Halides at Room Temperature

et al. 2017

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“…Ryu and co‐workers reported the radical‐type oxidative addition utilizing irradiation with a xenon lamp. In addition, Pd(II) species underwent geometric switch from square planar to tetrahedron under irradiation . Recently, Fu and co‐workers disclosed that, by employing blue‐LEDs irradiation with a dual phosphane ligand system, pd‐catalyzed Heck reactions of a diversity of unactivated 1 o , 2 o , and 3 o bromoalkanes with styrenetype substrates proceeded well at room temperature (Scheme ) …”

Section: Using Metal Catalysismentioning

confidence: 99%

Recent Developments in Radical‐Mediated Transformations of Organohalides

Lekkala

Balakrishna

et al. 2019

Eur J Org Chem

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In recent years, radical‐mediated transformations of organohalides, a class of powerful chemical transformations, have become an important field at the forefront of organic chemistry. Formation of free‐radicals from organohalides is among the most useful methods to access open‐shell reactive intermediates that have a number of established applications in chemical synthesis. Herein we summarize most of the strategies involving metal‐catalyzed, non‐metal‐catalyzed, as well as catalyst‐free radical‐mediated transformations of organohalides.

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A dual light-driven palladium catalyst: Breaking the barriers in carbonylation reactions

Torres

Liu

Arndtsen

2020

Science

224

140

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Transition metal–catalyzed coupling reactions have become one of the most important tools in modern synthesis. However, an inherent limitation to these reactions is the need to balance operations, because the factors that favor bond cleavage via oxidative addition ultimately inhibit bond formation via reductive elimination. Here, we describe an alternative strategy that exploits simple visible-light excitation of palladium to drive both oxidative addition and reductive elimination with low barriers. Palladium-catalyzed carbonylations can thereby proceed under ambient conditions, with challenging aryl or alkyl halides and difficult nucleophiles, and generate valuable carbonyl derivatives such as acid chlorides, esters, amides, or ketones in a now-versatile fashion. Mechanistic studies suggest that concurrent excitation of palladium(0) and palladium(II) intermediates is responsible for this activity.

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Solution Photochemistry and Kinetics of Palladium(II) Complexes

Cited by 3 publications

References 14 publications

Irradiation-Induced Heck Reaction of Unactivated Alkyl Halides at Room Temperature

Irradiation-Induced Heck Reaction of Unactivated Alkyl Halides at Room Temperature

Recent Developments in Radical‐Mediated Transformations of Organohalides

A dual light-driven palladium catalyst: Breaking the barriers in carbonylation reactions

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