Formal Bromine Atom Transfer Radical Addition of Nonactivated Bromoalkanes Using Photoredox Gold Catalysis

Zidan, Montserrat; McCallum, Terry; Swann, Rowan; Barriault, Louis

doi:10.1021/acs.orglett.0c03030

Cited by 28 publications

(25 citation statements)

References 87 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Alternatively, the non-linear Hammett relationship could suggest a change in the mechanism. Nickel has demonstrated the ability to undergo single-electron and two-electron oxidative addition processes. ,,, A change in oxidative addition mechanism could subsequently alter the mechanism of the following cyclization and C–I bond formation, which have been reported with other transition metals. ,− However, the concave-down shape of the plot along with the observed ρ-values suggests a change in the rate-determining step is more likely.…”

mentioning

confidence: 87%

Synthesis of Carbocyclic Compounds via a Nickel-Catalyzed Carboiodination Reaction

et al. 2021

View full text Add to dashboard Cite

A scalable nickel-catalyzed carboiodination reaction generating 6-membered carbocycles is reported. NiI 2 and P(OEt) 3 , as the ligand and reducing agent, provided decorated iodo-tetrahydronaphthalenes in up to 94% yield. The impact of varying electronic and steric parameters on the reaction are reported and a non-linear Hammett plot was obtained, supporting a change in the rate-determining step from oxidative addition to reductive elimination. Experimental and DFT studies suggest that the malonate group may stabilize a nickel oxidative-addition complex. A variety of heteroatom-containing nucleophiles and medicinally relevant heterocycles were easily incorporated into the products via simple S N 2 chemistry.

show abstract

mentioning

confidence: 87%

Synthesis of Carbocyclic Compounds via a Nickel-Catalyzed Carboiodination Reaction

et al. 2021

View full text Add to dashboard Cite

show abstract

“…459 In 2020 the same group reported the ATRC of unactivated alkyl bromides and aryl iodides (Scheme 95). 460 In general, ATRA and ATRC strategies require the use of electron deficient substrates (e.g., α-halocarbonyls, perfluoroalkyl halides) as standard alkyl halides are challenging due to their poor ability to sustain chain propagations by XAT. This methodology has therefore addressed a relevant synthetic and mechanistic challenge in the area.…”

Section: Metal-based Xat Reagentsmentioning

confidence: 99%

Applications of Halogen-Atom Transfer (XAT) for the Generation of Carbon Radicals in Synthetic Photochemistry and Photocatalysis

Hernández¹,

Constantin²,

2021

View full text Add to dashboard Cite

The halogen-atom transfer (XAT) is one of the most important and applied processes for the generation of carbon radicals in synthetic chemistry. In this review, we summarize and highlight the most important aspects associated with XAT and the impact it has had on photochemistry and photocatalysis. The organization of the material starts with the analysis of the most important mechanistic aspects and then follows a subdivision based on the nature of the reagents used in the halogen abstraction. This review aims to provide a general overview of the fundamental concepts and main agents involved in XAT processes with the objective of offering a tool to understand and facilitate the development of new synthetic radical strategies.

show abstract

“…Photocatalyzed atom transfer radical additions (PhATRAs) to olefins have been found with metal photocatalysts, such as the polypyridyl complexes of Ir- , and Ru-based photocatalysts, − Bi 2 O 3 , , Cu-derived complexes activated by light, − TiO 2 , and Au complexes in organic solvents. Nonmetal–organic photocatalysts, such as 4-methoxybenzaldehyde, , and light-activated halogen-bonding complexes , have also been reported to perform ATRA reactions.…”

Section: Radical Additions To Carbon–carbon Multiple Bonds In Aqueous...mentioning

confidence: 99%

Advances in Photocatalytic Organic Synthetic Transformations in Water and Aqueous Media

Barata‐Vallejo

Yerien

Postigo

2021

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

Advances in visible light-photocatalyzed preparative synthetic organic transformations in water or aqueous media are studied. Both the convenience of visible light photocatalytic strategies to achieve synthetic organic transformations and the employment of water or aqueous mixtures make this approach a very resourceful methodology. Mechanistic aspects for such photocatalyzed processes are discussed. The effects of water in the stereoselectivity of some reactions and considerations regarding the improved enantioselectivity in chiral catalytic photoredox reactions are manifested with the use of water. The use of water as a result of a protocol improvement or environmentally friendlier methodology as compared to the same reaction performed in organic solvents are also considered. All these combined effects of water as a reaction medium or its very presence in photocatalytic reactions have an ultimate goal which is to diminish the environmental impact of synthetic and photocatalytic processes. This perspective highlights the progress and state of the art organic transformations realized by photocatalytic techniques in water or aqueous systems as well as water as a reactant. In this regard, aromatic substitution reactions, radical additions to carbon–carbon double bonds, photooxidation reactions, decarboxylation processes, and miscellaneous reactions are presented.

show abstract

Formal Bromine Atom Transfer Radical Addition of Nonactivated Bromoalkanes Using Photoredox Gold Catalysis

Cited by 28 publications

References 87 publications

Synthesis of Carbocyclic Compounds via a Nickel-Catalyzed Carboiodination Reaction

Synthesis of Carbocyclic Compounds via a Nickel-Catalyzed Carboiodination Reaction

Applications of Halogen-Atom Transfer (XAT) for the Generation of Carbon Radicals in Synthetic Photochemistry and Photocatalysis

Advances in Photocatalytic Organic Synthetic Transformations in Water and Aqueous Media

Contact Info

Product

Resources

About