Regioselective Halogenation of Arenes and Heterocycles in Hexafluoroisopropanol

Tang, Ren‐Jin; Milcent, Thierry; Crousse, Benoı̂t

doi:10.1021/acs.joc.7b02920

Cited by 139 publications

(154 citation statements)

References 67 publications

Supporting

Mentioning

147

Contrasting

Unclassified

Order By: Relevance

“…The UV‐vis spectra and theoretical calculations indicated the formation of π‐complex intermediate of an arene with a nitronium ion, which was stabilized by HFIP. As another classic type of electrophilic substitution, electrophilic halogenation of arenes and heterocycles in HFIP has been disclosed by Crousse (Scheme b) . Readily available N‐halosuccinimides (NBS, NIS, and NCS) served as the halogenating reagents in the regioselective halogenation reaction.…”

Section: Electrophilic Reactionsmentioning

confidence: 99%

See 1 more Smart Citation

Fluorinated Alcohols: Magic Reaction Medium and Promoters for Organic Synthesis

Xiao

2019

The Chemical Record

111

View full text Add to dashboard Cite

Fluorinated alcohols have been widely used in the synthetic organic chemistry over the past decades. The unique properties such as the strong hydrogen‐bonding donor ability and low nucleophilicity allow them to promote organic reactions in the absence of any catalyst. These approaches have distinct advantages in terms of operational simplicity, practicability and environmental friendliness. Reactions promoted by fluorinated alcohols, including nucleophilic substitution reactions, annulation reactions, electrophilic reactions, dearomatization reactions, functionalization of multiple bond, epoxidation reactions and miscellaneous reactions have been summarized in this account.

show abstract

Section: Electrophilic Reactionsmentioning

confidence: 99%

“…2020, 20, 142 -161 halogenation of arenes and heterocycles in HFIP has been disclosed by Crousse (Scheme 24b). [45] Readily available Nhalosuccinimides (NBS, NIS, and NCS) served as the halogenating reagents in the regioselective halogenation reaction.…”

Section: P E R S O N a L A C C O U N T T H E C H E M I C A L R E C O R Dmentioning

confidence: 99%

Fluorinated Alcohols: Magic Reaction Medium and Promoters for Organic Synthesis

Xiao

2019

The Chemical Record

111

View full text Add to dashboard Cite

show abstract

“…However, majority of these procedures require added catalysts, oxidants, nonconventional solvents, reagents or large reaction times were occasionally operated at harsh conditions. Most recently, NBS/PhSSPh (or PhSSiMe 3 ) [19], NBS/indoles [20], NBS/hexafluoroisopropanol [21], NBS/I 2 [22], NaBr/ H 2 O 2 /AcOH [23] and 1,2-ethanediylbis(triphenylphosph onium)-ditribromide [24] were found attractive. Nevertheless, these also suffer with the necessity of catalysts, expensive solvents, oxidants or large reaction times.…”

Section: Introductionmentioning

confidence: 99%

Added catalyst-free, versatile and environment beneficial bromination of (hetero)aromatics using NBS in WEPA

et al. 2019

View full text Add to dashboard Cite

The aromatic or heteroaromatic bromides are the quite common substrates in several organic transformations. The synthesis of arylbromides is challenging and required expensive catalytic systems or problematic organic solvents. This article unveils an environment beneficial, versatile and facile procedure for the synthesis of aryl/heteroaryl bromides using N-bromosuccinimide in water extract of pomegranate ash. The preparation of bromoarenes or bromoheteroarenes was accomplished under atmospheric conditions in the absence of added catalyst, promoter, problematic solvent and additives. The products were formed with greater rates in very high to quantitative yields using biowaste derived media shows the environmental benefits like utilization of waste, safer media, rich chemical economy, economic feasibility and dwindling the chemical waste, has eventual scope towards further explorations.

show abstract

“…[9][10][11][12][13] In particular, solvent control enables distinct selectivity, wherein protic media, such as 1,1,1,3,3,3-hexauoroisopropanol (HFIP), outperform others. 14,15 To improve the morphology and allowing other design options instead of the limited geometries of BDD, together with a less costly anode material, we investigated different transition metals and their alloys with regards to their applicability in electrochemical conversions. Leaded bronze enabled the selective and high yielding dehalogenation reaction of cyclopropanes.…”

mentioning

confidence: 99%

About the selectivity and reactivity of active nickel electrodes in C–C coupling reactions

et al. 2020

View full text Add to dashboard Cite

Active anodes which are operating in highly stable protic media such as 1,1,1,3,3,3-hexafluoroisopropanol are rare. Nickel forms, within this unique solvent, a non-sacrificial active anode at constant current conditions, which is superior to the reported powerful molybdenum system. The reactivity for dehydrogenative coupling reactions of this novel active anode increases when the electrolyte is not stirred during electrolysis. Besides the aryl-aryl coupling, a dehydrogenative arylation reaction of benzylic nitriles was found while stirring the mixture providing quick access to synthetically useful building blocks.Scheme 2 Benzylic dehydrogenative cross-coupling of 2-aryl acetonitrile (1l) and arenes 3 by anodic treatment. Hydrogen atoms of the X-ray single crystal structure analysis of 4d were removed for clarity. Conditions: Nikgraphite 0.1 M NBu 4 PF 6 in HFIP 7.5 mA cm À2 , 3.0 F. This journal is

show abstract

Regioselective Halogenation of Arenes and Heterocycles in Hexafluoroisopropanol

Cited by 139 publications

References 67 publications

Fluorinated Alcohols: Magic Reaction Medium and Promoters for Organic Synthesis

Fluorinated Alcohols: Magic Reaction Medium and Promoters for Organic Synthesis

Added catalyst-free, versatile and environment beneficial bromination of (hetero)aromatics using NBS in WEPA

About the selectivity and reactivity of active nickel electrodes in C–C coupling reactions

Contact Info

Product

Resources

About