The Cleavage of Three-Membered Ring Compounds by Transition Metal Organometallic Complexes

1981 ◽  
Vol 21 (2-3) ◽  
pp. 203-209 ◽  
Author(s):  
Howard Alper
Keyword(s):  
Transition Metal ◽  
Membered Ring ◽  
Organometallic Complexes ◽  
Ring Compounds

Transition-Metal-Free Ring Expansion Reactions of Indene-1,3-dione: Synthesis of Functionalized Benzoannulated Seven-Membered Ring Compounds

2018 ◽  
Vol 20 (7) ◽  
pp. 1744-1747 ◽  
Author(s):  
Qiyi Yao ◽  
Lingkai Kong ◽  
Mengdan Wang ◽  
Yang Yuan ◽  
Ruizhuo Sun ◽  
...  
Keyword(s):  
Transition Metal ◽  
Ring Expansion ◽  
Membered Ring ◽  
Free Ring ◽  
Metal Free ◽  
Ring Compounds

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>

scholarly journals Low-valent dialkoxytitanium(ii): a useful tool for the synthesis of functionalized seven-membered ring compounds

2021 ◽  
Vol 57 (29) ◽  
pp. 3603-3606
Author(s):  
Florent Bodinier ◽  
Youssouf Sanogo ◽  
Janick Ardisson ◽  
Marie-Isabelle Lannou ◽  
Geoffroy Sorin
Keyword(s):  
Grignard Reagent ◽  
Membered Ring ◽  
Ring Compounds ◽  
Low Valent

Herein, we describe unprecedented access to all-carbon or heterocyclic seven-membered ring frameworks from 1,8-ene-ynes promoted by inexpensive low-valent titanium(ii) species, readily available from a combination of Ti(OiPr)4 and Grignard reagent.

Enantioselective Functionalization of Prochiral Cyclobutanones and Cyclobutenones

Synlett ◽  
2021 ◽  
Author(s):  
Memg Wang ◽  
Changxu Zhong ◽  
Ping Lu
Keyword(s):  
Asymmetric Synthesis ◽  
Membered Ring ◽  
Enantioselective Synthesis ◽  
Ring Compounds ◽  
Recent Advances ◽  
Cyclobutane Derivatives

Enantioselective synthesis of cyclobutane derivatives is still a challenging topic in asymmetric synthesis. [2+2]-Cycloaddition and skeleton rearrangement are two primary strategies to this end. Recently, functionalization of cyclobutanones and cyclobutenones, which are readily available via [2+2]-cycloadditions as prochiral substrates, has emerged as a powerful tool to access versatile four-membered ring compounds. Herein, we summarize some recent advances in these areas from our and other groups.

Transition metal NMR chemical shifts and polarizability effect in organometallic complexes

2009 ◽  
Vol 47 (9) ◽  
pp. 782-790 ◽  
Author(s):  
Alexey N. Egorochkin ◽  
Olga V. Kuznetsova ◽  
Nadiya M. Khamaletdinova ◽  
Yury A. Kurskii ◽  
Lada G. Domratcheva-Lvova ◽  
...  
Keyword(s):  
Transition Metal ◽  
Chemical Shifts ◽  
Organometallic Complexes ◽  
Nmr Chemical Shifts ◽  
Polarizability Effect
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