Facile chelate-assisted carbon-halogen bond cleavage at tungsten(0)

1987 ◽  
Vol 6 (9) ◽  
pp. 1995-1996 ◽  
Author(s):  
Thomas G. Richmond ◽  
Margaret A. King ◽  
Eric P. Kelson ◽  
Atta M. Arif
Keyword(s):  
Halogen Bond ◽  
Bond Cleavage

scholarly journals Computational study on the mechanism of metal-free photochemical borylation of aryl halides

2021 ◽  
Author(s):  
Chenhao Tu ◽  
Nana Ma ◽  
Qingli Xu ◽  
Wenyue Guo ◽  
Lanxin Zhou ◽  
...  
Keyword(s):  
Density Functional ◽  
Uv Light ◽  
Computational Study ◽  
Halogen Bond ◽  
Bond Cleavage ◽  
Aryl Halides ◽  
Homolytic Cleavage ◽  
Functional Theory ◽  
Aryl Radicals

C-radical borylation is an significant approach for the construction of carbon−boron bond. Photochemical borylation of aryl halides successfully applied this strategy. However, precise mechanisms, such as the generation of aryl radicals and the role of base additive(TMDAM) and water, remain controversy in these reactions. In this study, photochemical borylation of aryl halides has been researched by density functional theory (DFT) calculations. Indeed, the homolytic cleavage of the C−X bond under irradiation with UV-light is a key step for generation of aryl radicals. Nevertheless, the generation of aryl radicals may also undergo the process of single electron transfer and the heterolytic carbon-halogen bond cleavage sequence, and the latter is favorable during the reaction.

Au@Pd Bimetallic Nanocatalyst for Carbon–Halogen Bond Cleavage: An Old Story with New Insight into How the Activity of Pd is Influenced by Au

2018 ◽  
Vol 52 (7) ◽  
pp. 4244-4255 ◽  
Author(s):  
Rui Liu ◽  
Hui-min Chen ◽  
Li-ping Fang ◽  
Cuihong Xu ◽  
Zuoliang He ◽  
...  
Keyword(s):  
Halogen Bond ◽  
Bond Cleavage ◽  
Bimetallic Nanocatalyst ◽  
Insight Into

Hot Electron-Induced Carbon–Halogen Bond Cleavage Monitored by in Situ Surface-Enhanced Raman Spectroscopy

2019 ◽  
Vol 123 (27) ◽  
pp. 16741-16746 ◽  
Author(s):  
Ping Jiang ◽  
Yueyue Dong ◽  
Ling Yang ◽  
Yaran Zhao ◽  
Wei Xie
Keyword(s):  
Raman Spectroscopy ◽  
Halogen Bond ◽  
Bond Cleavage ◽  
Surface Enhanced Raman Spectroscopy ◽  
Hot Electron ◽  
Surface Enhanced ◽  
Surface Enhanced Raman

Iminyl-Radical-Triggered C–C Bond Cleavage of Cycloketone Oxime Derivatives: Generation of Distal Cyano-Substituted Alkyl Radicals and Their Functionalization

Synthesis ◽  
2020 ◽  
Vol 52 (11) ◽  
pp. 1585-1601 ◽  
Author(s):  
Tiebo Xiao ◽  
Lei Zhou ◽  
Hongtai Huang ◽  
Devireddy Anand
Keyword(s):  
Halogen Bond ◽  
Cyano Group ◽  
Bond Cleavage ◽  
Bond Formation ◽  
Radical Reaction ◽  
Building Blocks ◽  
Aromatic Rings ◽  
Organometallic Reagents ◽  
Alkyl Radicals ◽  
Oxime Derivatives

Alkyl nitriles are versatile building blocks in organic synthesis because the cyano group can be easily converted into other functional groups. Iminyl-radical-triggered C–C bond cleavage of cycloketone oxime­ derivatives provides a practical route to access distal cyano-substituted alkyl radicals, which has given chemists a new radical reaction platform for the synthesis of diverse alkyl nitriles. This review provides an overview of various types of radical cyanoalkylation via ring opening of cycloketone oxime derivatives.1 Introduction2 C–C Bond Formation2.1 Alkenes as Radical Acceptors2.2 Aromatic Rings as Radical Acceptors2.3 Organometallic Reagents as Radical Acceptors2.4 Cyanoalkyl-Radical-Triggered Cyclization Reactions2.5 Miscellaneous3 C–Heteroatom Bond Formation3.1 C–O Bond Formation3.2 C–N Bond Formation3.3 C–S Bond Formation3.4 C–Halogen Bond Formation3.5 C–B Bond Formation4 Conclusion

Carbon-halogen bond cleavage energies of polyhaloalkyl radical anions in solution

1996 ◽  
Vol 37 (9) ◽  
pp. 1457-1460 ◽  
Author(s):  
Jin-Pei Cheng ◽  
Zirong Zheng
Keyword(s):  
Halogen Bond ◽  
Bond Cleavage ◽  
Radical Anions

Visible Light-Promoted Metal-Free Reduction of Organohalides by 2-Naphthyl or 2-Hydroxynaphthyl-Substituted 1,3-Dimethylbenzimidazolines

2015 ◽  
Vol 68 (11) ◽  
pp. 1648 ◽  
Author(s):  
Eietsu Hasegawa ◽  
Kazuma Mori ◽  
Shiori Tsuji ◽  
Kazuki Nemoto ◽  
Taku Ohta ◽  
...  
Keyword(s):  
Visible Light ◽  
Halogen Bond ◽  
Light Emitting Diode ◽  
Bond Cleavage ◽  
Ring Expansion ◽  
Single Electron Transfer ◽  
Reduction Reactions ◽  
Light Emitting ◽  
Reducing Ability ◽  
Carbon Radicals

The visible light-promoted reduction reactions of some organohalides were investigated using 2-aryl-1,3-dimethylbenzimidazolines (Ar-DMBIH) possessing 2-naphthyl or 2-hydroxynaphthyl substituents. In these reduction reactions, single-electron transfer from photo-excited Ar-DMBIH, attained by Xe lamp irradiation through an appropriate glass-filter (λ > 390 nm), to the halide substrates leads to the carbon–halogen bond cleavage, followed by the rearrangements of the formed carbon radicals such as 5-exo hexenyl cyclization and the Dowd–Beckwith ring expansion. Addition of 1,8-diazabicyclo[5.4.0]undec-7-ene was found to enhance the reducing ability of hydroxynaphthyl-substituted DMBIH. A household white light-emitting diode was also used as a light source for these reactions.

Photochemistry of organohalogeno-compounds. Part XIX the effect of fluorine on photochemical carbon-halogen bond cleavage

1987 ◽  
Vol 34 (3-4) ◽  
pp. 313-322 ◽  
Author(s):  
A. Gregorčič ◽  
M. Zupan
Keyword(s):  
Halogen Bond ◽  
Bond Cleavage

Photochemistry of α-chloro- and α-bromoacetophenone. Determination of extinction coefficients for halogen–benzene complexes

1988 ◽  
Vol 66 (6) ◽  
pp. 1474-1478 ◽  
Author(s):  
W. G. McGimpsey ◽  
J. C. Scaiano
Keyword(s):  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Benzene Solution ◽  
Halogen Bond ◽  
Bond Cleavage ◽  
Laser Flash ◽  
Quantum Yields ◽  
Extinction Coefficients ◽  
Transient Data

The photochemical dehalogenation of α-haloacetophenones (Cl, Br) in benzene solution has been examined under conditions of continuous and pulsed laser irradiation. Product and quantum yield studies indicate that carbon-halogen bond cleavage occurs with quantum yields of 0.88 and 0.41 for α-chloro- and α-bromoacetophenone, respectively. These values are based on trapping studies in which the PhC(O)ĊH2 radicals produced photochemically are scavenged by hydrogen donors such as benzenethiol. Laser flash photolysis studies lead to intense transient signals due to benzene–halogen complexes. Combination of transient data and quantum yields lead to extinction coefficients of 1 800 and 23 700 M−1 cm−1 for the chlorine (490 nm) and bromine (550 nm) complexes, respectively.

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