Electron transfer in nucleophilic vinyl substitution reactions involving bromovinyl sulfones

1981 ◽  
Vol 30 (12) ◽  
pp. 2320-2322 ◽  
Author(s):  
E. A. Berdnikov ◽  
A. A. Vafina ◽  
V. L. Polushina ◽  
R. M. Zaripova ◽  
F. R. Tantasheva ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Substitution Reactions ◽  
Nucleophilic Vinyl Substitution

Substitution of Bridgehead Halogens by a Free-Radical Electron-Transfer Mechanism

1996 ◽  
Vol 49 (5) ◽  
pp. 581 ◽  
Author(s):  
MC Harsanyi ◽  
PA Lay ◽  
RK Norris ◽  
PK Witting
Keyword(s):  
Electron Transfer ◽  
Nitro Group ◽  
Intramolecular Electron Transfer ◽  
Substitution Reactions ◽  
Radical Chain ◽  
Electron Transfer Mechanism ◽  
Regioselective Substitution ◽  
Leaving Group ◽  
Aromatic Nitro ◽  
Bridgehead Position

The reactions of 1-bromo-7-nitro- and 1-bromo-6-nitro-1,4-methanonaphthalene (2) and (3), and 9-bromo-2-nitro, 10-bromo-2-nitro-, 9,10-dibromo-2-nitro- and 9,10-diiodo-2-nitro-9,10-ethano-9,10-dihydroanthracene (4)-(7). respectively, with the sodium salt (1) of p-toluenethiol gave substitution products that were shown to be formed by an SRN1 or a related radical chain mechanism. In the relatively slow substitution reactions of the salt (1) with compounds (2)-(5). That contain bromine at bridgehead positions that are either meta- or para-benzylic to an aromatic nitro group, the rates of substitution in the isomers where the leaving group was meta- benzylic to the aromatic nitro group were slightly greater than those for the corresponding para-benzylic isomer. In compounds (6)and (7) the halogens are at bridgehead positions that are either meta- or para-benzylic relative to an aromatic nitro group within the same molecule. In the case of the reaction of the dibromide (6) with the thiolate (1), substitution was slow and occurred more rapidly at the benzylic -bridgehead position meta to the nitro group than at the corresponding para-benzylic position. In contast , the reaction of the diiodide (7) with the thiolate (1) gave substitution products which formed more rapidly than in the corresponding reaction of the dibromide (6) and the regioselectivity was reversed, with substitution occurring more readily at the bridgehead position para-benzylic to the nitro group than at the corresponding meta- benzylic position. The ratio of meta to para substitution products, determined for the reactions of compounds (2)-(6) with the salt (1), were in the range 1.15-2.5:1, while the reaction of (7) with the same nucleophile afforded a meta-to-para ratio of 1:2:3. These ratios contrast not only with each other, but also with the differences in reactivities determined for other nitrobenzylic systems, which are known to undergo SRN1 substitution reactions with the same nucleophile. The differences in first, the regioselectivity of substitution between the bridgehead systems, and secondly, the differences in the observed rates of regioselective substitution are compared with other simple nitrobenzylic halides. These differences are rationalized in terms of the effect of fixing the C-X bond at a bridgehead position to be orthogonal with the plane of the nitroaromatic group; this results in a reduction of the rate constants of intramolecular electron transfer, with significant consequences on the detailed overall mechanism for these reactions.

Nucleophilic Substitution Reactions by Electron Transfer

ChemInform ◽  
2003 ◽  
Vol 34 (17) ◽  
Author(s):  
Roberto A. Rossi ◽  
Adriana B. Pierini ◽  
Alicia B. Penenory
Keyword(s):  
Electron Transfer ◽  
Nucleophilic Substitution ◽  
Substitution Reactions ◽  
Nucleophilic Substitution Reactions

ChemInform Abstract: Substitution Reactions which Proceed via Radical Anion Intermediates. Part 32. Electron-Transfer Substitution Reactions: Leaving Groups.

ChemInform ◽  
1988 ◽  
Vol 19 (39) ◽  
Author(s):  
N. KORNBLUM ◽  
P. ACKERMANN ◽  
J. W. MANTHEY ◽  
M. T. MUSSER ◽  
H. W. PINNICK ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Radical Anion ◽  
Substitution Reactions ◽  
Leaving Groups
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