Regioselective Fluoroalkylarylation of Enamides Enabled by an Iron-Catalyzed Multicomponent Radical Cross-Coupling Strategy DOI Creative Commons
Ángel Rentería‐Gómez,

Macayla Guerrero,

Mireya Ramirez-Lopez

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(40), P. 7440 - 7445

Published: Sept. 29, 2023

Fluoroalkylated compounds are important entities in agrochemicals, pharmaceuticals, and materials. The catalytic dicarbofunctionalization of alkenes represents a powerful strategy for the rapid construction diversification compounds. In this vein, multicomponent cross-coupling reactions (MC-CCR) can provide an efficient synthetic route to build molecular complexity. work, we report first iron-catalyzed three-component fluoroalkylarylation enamides via selective formation trapping α-amide radicals under mild conditions fast reaction times. tolerates variety commercially available aryl Grignard reagents fluoroalkyl halides. Finally, use removable phthalimido group provides prepare highly valuable γ-difluoroalkylated amines.

Language: Английский

Nickel-Catalyzed Modular Four-Component 1,4-Alkylcarbonylation of 1,3-Enynes to Tetra-Substituted CF3–Allenyl Ketones DOI

Qi-Chao Shan,

Yan Zhao, Shutao Wang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(4), P. 2144 - 2150

Published: Jan. 25, 2024

The modular four-component carbonylation of unsaturated hydrocarbons represents an elegant strategy for the one-pot synthesis complex carbonyl compounds. However, this is currently focused on 1,2-difunctionalization olefins or alkynes, and 1,4-alkylcarbonylation 1,3-enynes remains unexplored. In study, we report a Ni-catalyzed CF3-containing under 1 atm CO, which affords tetra-substituted CF3-allenyl ketones with good yields selectivity. This protocol features mild conditions, broad substrate scope, acceptable functional group compatibility. Control experiments revealed that reactivity oxime esters (regulated by leaving groups) polarity matching are crucial success cascade. Preliminary mechanistic studies suggest acyl nickel key intermediate in transformation.

Language: Английский

Citations

27

Nickel-Catalyzed Carbonylative Negishi Cross-Coupling of Unactivated Secondary Alkyl Electrophiles with 1 atm CO Gas DOI

Yetong Zhang,

Qihang Cao,

Yang Xi

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(12), P. 7971 - 7978

Published: March 14, 2024

We describe a nickel-catalyzed carbonylative cross-coupling of unactivated secondary alkyl electrophiles with the organozinc reagent at atmospheric CO gas, thus allowing expedient construction unsymmetric dialkyl ketones broad functional group tolerance. The leverage newly developed

Language: Английский

Citations

17

Recent Advances in Nickel Catalyzed Carbonylative Reactions via the Insertion of Carbon Monoxide DOI
Xinzhou Chen, Gang Chen, Zhong Lian

et al.

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 42(2), P. 177 - 189

Published: Sept. 4, 2023

Comprehensive Summary Carbonyl compounds have attracted considerable attention due to their extensive applications in drug discovery. Furthermore, they are important synthetic intermediates for the construction of carbon‐carbon and carbon‐heteroatom bonds. Transition‐metal‐catalyzed carbonylation via insertion CO is one most efficient straightforward strategies access carbonyl compounds. However, transition‐metal‐catalyzed carbonylative reactions require expensive toxic noble‐metal catalysts. Therefore, there a growing demand exploration nickel‐catalyzed earth abundance low cost nickel. Compared with well‐established palladium‐catalyzed reactions, analogous transformations been relatively underdeveloped. This primarily because strongly binds nickel, often resulting catalyst poisoning. In recent years, some research groups focused on using surrogates or NN 2 pincer nickel circumvent formation Ni(CO) 4 . Nickel‐catalyzed has applied carbonyl‐containing compounds, such as ketones, carboxylic acids, thioesters, acyl chloride carboxamides.

Language: Английский

Citations

23

Manganese-Catalyzed Carbonylation of Unactivated Alkyl Bromides with Alkylidenecyclopropanes DOI

Peng-Rui Liu,

Miao-Miao Ji,

Jian-Bang Hu

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(12), P. 9487 - 9495

Published: June 7, 2024

Language: Английский

Citations

8

Nickel-catalyzed multicomponent 1,4-fluoroalkylcarbonylation of 1,3-enynes to access allenyl ketones DOI

Bing‐Hong Teng,

Chang‐Sheng Kuai, Yingying Zhao

et al.

Tetrahedron, Journal Year: 2024, Volume and Issue: 157, P. 133965 - 133965

Published: March 28, 2024

Language: Английский

Citations

6

Reversal of the Regioselectivity of Iron‐Promoted Hydrogenation and Hydrohalogenation of gem‐Difluoroalkenes DOI
Yuyang Zhang, Yuchen Zhang, Xiao‐Song Xue

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(25)

Published: April 19, 2024

The reaction regioselectivity of gem-difluoroalkenes is dependent on the intrinsic polarity. Thus, reversal addition remains a formidable challenge. Herein, we described an unprecedented hydrogen atom transfer (HAT) to triggered by Fe-H species for formation difluoroalkyl radicals. Hydrogenation in situ generated radicals gave difluoromethylated products. Mechanism experiments and theoretical studies revealed that kinetic effect irreversible HAT process resulted this scenario, leading less stable α-difluoroalkyl radical regioisomer. On basis new gem-difluoroalkene, iron-promoted hydrohalogenation efficient synthesis aliphatic chlorodifluoromethyl-, bromodifluoromethyl- iododifluoromethyl-containing compounds was developed. Particularly, novel provided large-scale access various iododifluoromethylated high value synthetic application.

Language: Английский

Citations

6

Nickel-catalyzed acylzincation of allenes with organozincs and CO DOI Creative Commons
Xianqing Wu, Chenglong Wang, Ning Liu

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Oct. 31, 2023

Transition metal-catalyzed carbonylative reaction with CO gas are among the central task in organic synthesis, enabling construction of highly valuable carbonyl compound. Here, we show an earth-abundant nickel-catalyzed three-component tandem acylzincation/cyclization sequence allene and alkylzinc reagent 1 atm under mild conditions. This protocol is featured by broad functional group tolerance high selectivity, providing a rapid convenient synthetic method for diverse fully substituted benzotropone derivatives. Mechanistic studies reveal that installation cyano tethered to moiety enables regio- stereoselectivity this acylzincation allene, allowing selective formation three consecutive C-C bonds efficient manner.

Language: Английский

Citations

13

Iron-Catalyzed Regioselective Reductive Fluoroalkylalkenylation of Unactivated Alkenes DOI
Siyu Wang,

Bohao Guo,

Tong Mu

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(3), P. 1575 - 1583

Published: Jan. 16, 2024

The example of iron-catalyzed reductive fluoroalkylalkenylation unactivated alkenes has been disclosed, affording the stereodefined homoallylic fluoroalkanes with high efficiency and regioselectivity. This three-component cross-electrophile coupling features directing groups free, good functional group tolerance, broad substrate scope, late-stage difunctionalization biorelevant molecules. Moreover, this protocol sheds light on distinct reactivity disparities between fluoroalkyl nonfluoroalkyl radicals in cross-coupling reactions, highlighting unique nature iron/B2pin2 systems.

Language: Английский

Citations

5

Enantioselective Palladium-Catalyzed Domino Carbonylative Heck Esterification of o-Iodoalkenylbenzenes with Arylboronic Acids DOI

Yaodu Zhang,

Ming Chen, Yang Li

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(45), P. 8110 - 8115

Published: Nov. 3, 2023

The current investigation presents an innovative palladium-catalyzed asymmetric carbonylative Heck esterification method. This approach facilitates the efficient synthesis of various chiral γ-ketoacid esters by utilizing o-alkenyliodobenzenes and arylboronic acids as primary substrates. reaction achieves creation three carbon–carbon bonds, two carbon–oxygen establishment a quaternary carbon center within single step. α-chiral were obtained in yields ranging from good to high yields, displaying enantiomeric excesses (ee's) levels up 92% under mild conditions.

Language: Английский

Citations

10

Nickel-catalyzed carbonylative four-component 1,4-dicarbofunctionalization of 1,3-enynes DOI

Zhao Yan,

Qi-Chao Shan,

Xin Hong

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(6), P. 2029 - 2038

Published: April 24, 2024

Language: Английский

Citations

4