A novel electrophilic rearrangement with migration of an alkoxycarbonyl group from carbon to a nitrogen anionic center

1998 ◽  
Vol 47 (9) ◽  
pp. 1832-1833 ◽  
Author(s):  
Yu. G. Gololobov ◽  
M. A. Galkina ◽  
I. Yu. Kuz'mintseva ◽  
P. V. Petrovskii
Keyword(s):  
Anionic Center ◽  
Electrophilic Rearrangement

Intramolecular ring opening of a 2,3-epoxy alcohol by a xanthate anionic center; stereospecific preparation of 2-mercapto-1,3-diol units

1994 ◽  
Vol 5 (1) ◽  
pp. 51-60 ◽  
Author(s):  
Jun'ichi Uenishi ◽  
Mitsuhiro Motoyama ◽  
Yoshitaka Nishiyama ◽  
Yuichi Hirota ◽  
Yuki Kubo ◽  
...  
Keyword(s):  
Ring Opening ◽  
Epoxy Alcohol ◽  
Anionic Center ◽  
Intramolecular Ring

ChemInform Abstract: A New Electrophilic Rearrangement.

ChemInform ◽  
2010 ◽  
Vol 27 (32) ◽  
pp. no-no
Author(s):  
V. KONECNY ◽  
S. KOVAC
Keyword(s):  
Electrophilic Rearrangement

The Effect of Structural Changes on the Polarizability and Second Hyperpolarizability in Some Benzene Isomers and Their Anions

1985 ◽  
Vol 40 (2) ◽  
pp. 142-148 ◽  
Author(s):  
J. Waite ◽  
M. G. Papadopoulos
Keyword(s):  
Structural Changes ◽  
Substituent Effects ◽  
Lone Pair ◽  
Second Hyperpolarizability ◽  
Hartree Fock ◽  
Anionic Center ◽  
Homo Lumo ◽  
Single Bonds

The polarizability and second hyperpolarizability of fulvene, dimethylene-cyclobutene, trimethylene- cyclopropane, bicyclopentadiene-propane, bicyclopentadiene-propene, Dewar benzene, benzvalene and several of their anions are computed, employing a CNDO coupled Hartree-Fock procedure. The interaction of the lone pair on the anionic center with double and single bonds, the HOMO-LUMO gap, and substituent effects are employed to illuminate the structurepolarization relationship. An approximate, computationally found formula for the second hyperpolarizability is proposed.

ChemInform Abstract: Intramolecular Ring Opening of a 2,3-Epoxy Alcohol by a Xanthate Anionic Center; Stereospecific Preparation of 2-Mercapto-1,3-diol Units.

ChemInform ◽  
2010 ◽  
Vol 26 (10) ◽  
pp. no-no
Author(s):  
J. UENISHI ◽  
M. MOTOYAMA ◽  
Y. NISHIYAMA ◽  
Y. HIROTA ◽  
Y. KUBO ◽  
...  
Keyword(s):  
Ring Opening ◽  
Epoxy Alcohol ◽  
Anionic Center ◽  
Intramolecular Ring

Redox-Neutral α-Arylation of Alkyl Nitriles with Aryl Sulfoxides: A Rapid Electrophilic Rearrangement

2017 ◽  
Vol 139 (11) ◽  
pp. 4211-4217 ◽  
Author(s):  
Li Shang ◽  
Yonghui Chang ◽  
Fan Luo ◽  
Jia-Ni He ◽  
Xin Huang ◽  
...  
Keyword(s):  
Electrophilic Rearrangement

ChemInform Abstract: Novel Intramolecular Electrophilic Rearrangement: Migration of Alkoxycarbonyl Group from Carbon Atom to an Anionic Nitrogen Center.

ChemInform ◽  
2010 ◽  
Vol 29 (52) ◽  
pp. no-no
Author(s):  
YU. G. GOLOLOBOV ◽  
M. A. GALKINA ◽  
I. YU. KUZ'MINTSEVA ◽  
P. V. PETROVSKII
Keyword(s):  
Carbon Atom ◽  
Nitrogen Center ◽  
Electrophilic Rearrangement

Cycloproparenyl anions: From models to real systems

2005 ◽  
Vol 77 (11) ◽  
pp. 1835-1850 ◽  
Author(s):  
Mirjana Eckert-Maksic ◽  
Zoran Glasovac
Keyword(s):  
Aromatic Ring ◽  
Linear Extension ◽  
Resonance Effect ◽  
Lone Pair ◽  
Membered Ring ◽  
Electron Interaction ◽  
Anionic Center ◽  
Cyano Groups ◽  
Opposing Effects ◽  
The Impact

An overview of our recent work on cycloproparenyl anions is given. Preparation, the electronic structure, and the properties of the progenitor of the series, cyclopropabenzenyl anion, are discussed. It is shown that the cyclopropabenzenyl anion is by ca. 145 kJ mol-1 more stable than the parent cyclopropenyl anion according to results of the MP2/6-31+G(d) calculations. This finding was attributed to a delicate balance of two opposing effects: (a) propensity of the aromatic ring to alleviate unfavorable 4π electron interaction within the three-membered ring by the anionic resonance effect and (b) a pyramidalization of the anionic center, which tends to maximize the s-character of the lone pair. We have also shown that stability of the cyclopropabenzenyl anion could be considerably enhanced by substitution of the aromatic ring with fluorine and cyano groups, as well as by a linear extension of the aromatic backbone. Finally, the impact of the fusion of additional cyclopropenyl ring to the benzene moiety to acidity of the benzylic position in cyclopropabenzene is discussed.

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