Rh-Catalyzed C–H bond alkylation of indoles with α,α-difluorovinyl tosylate via indolyl group migration

2018 ◽  
Vol 54 (44) ◽  
pp. 5618-5621 ◽  
Author(s):  
Lu Zhou ◽  
Chuan Zhu ◽  
Teck-Peng Loh ◽  
Chao Feng
Keyword(s):  
Group Migration ◽  
Group Shift

An unprecedented C–H alkylation of indoles was achieved with α,α-difluorovinyl tosylate through an indolyl group shift process enabled by fluorine substituents.

Isomerization of the Isoprene Hydroxy Nitrates and Formation of Orthonitrite Compounds

2019 ◽  
Author(s):  
Gabriel da Silva
Keyword(s):  
Hydroxy Group ◽  
Peroxyl Radical ◽  
Branching Fractions ◽  
Membered Ring ◽  
Low Energy ◽  
Peroxyl Radicals ◽  
Aerosol Formation ◽  
Subsequent Removal ◽  
Ring Compounds ◽  
Group Migration

Atmospheric oxidation of isoprene produces significant yields of eight unique nitrate 11 compounds, each with a β- or δ-hydroxy group. These isoprene hydroxy nitrates (ISOPNs) 12 significantly impact upon global NOx budgets, O3 levels, and aerosol formation. 13 Uncertainties exist, however, in our understanding of ISOPN chemistry, particularly in their 14 yields from the reaction of isoprene peroxyl radicals with NO. This study describes novel 15 isomerization reactions of the ISOPNs, identified through the application of computational 16 chemistry techniques. These reactions produce saturated polycyclic orthonitrite compounds 17 via attack of the R–NO2 group on the vinyl moiety. For the δ-hydroxy nitrates, low-energy 18 isomerization pathways exist to six-membered ring compounds that are around 5 kcal mol-1 19 exothermic. These reactions proceed with barriers around 15 kcal mol-1 below the 20 respective peroxyl radical + NO reactants and yield orthonitrites that can further isomerize 21 to β-hydroxy ISOPNs. Moreover, the δ-hydroxy nitrates can directly interconvert with their β 22 substituted counterparts via NO3 group migration, with barriers that are lower yet. It follows 23 that β-hydroxy nitrates may be stabilized in the δ-hydroxy form, and vice versa. Moreover, 24 the lowest-energy pathway for dissociation of the δ-hydroxy ISOPNs is for the formation of 25 β-hydroxy alkoxyl radicals, and because of this established branching fractions between the 26 various isoprene peroxyl radicals may require re-evaluation. The results presented here also 27 suggest that ISOPNs may be stabilized to some extent in their saturated orthonitrite forms, 28 which has implications for both the total nitrate yield and for their subsequent removal by 29 OH, O3, and photolysis.<br><br>

Group-Shift and the Consensus Effect

2016 ◽  
Author(s):  
David Dillenberger ◽  
Collin Raymond
Keyword(s):  
Group Shift

scholarly journals Kinetic Studies of Acetyl Group Migration between the Saccharide Units in an Oligomannoside Trisaccharide Model Compound and a Native Galactoglucomannan Polysaccharide

ChemBioChem ◽  
2021 ◽  
Author(s):  
Robert Lassfolk ◽  
Sara Bertuzzi ◽  
Ana Ardá ◽  
Johan Wärnå ◽  
Jesús Jiménez‐Barbero ◽  
...  
Keyword(s):  
Model Compound ◽  
Kinetic Studies ◽  
Acetyl Group ◽  
Group Migration

A trimethylsilyl group migration in the chemistry of η5-C5H5Fe(CO)2SiMe3

1981 ◽  
Vol 221 (2) ◽  
pp. 143-146 ◽  
Author(s):  
Stuart R. Berryhill ◽  
Brett Sharenow
Keyword(s):  
Trimethylsilyl Group ◽  
Group Migration

ChemInform Abstract: Chemical Origins of Substituent Effects in Alkylpentacarbonylmanganese(I) Group Migration Reactions.

ChemInform ◽  
1988 ◽  
Vol 19 (40) ◽  
Author(s):  
F. U. AXE ◽  
D. S. MARYNICK
Keyword(s):  
Substituent Effects ◽  
Group Migration

Rhodium‐Catalyzed Atroposelective Access to Axially Chiral Olefins via C‐H Bond Activation and Directing Group Migration

2021 ◽  
Author(s):  
Xingwei Li ◽  
Ruijie Mi ◽  
Xukai Zhou ◽  
Haohua Chen ◽  
Yu Lan ◽  
...  
Keyword(s):  
Bond Activation ◽  
Axially Chiral ◽  
Directing Group ◽  
Group Migration
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