Level 1 – Case 9
Solvolysis of Electron-Deficient Norbornyl
Triflates
Key point: Reaction Intermediates: Carbocations
X
X
H
OTf
X
X
X
X
X
f
OTf
H
X
solvolysis of
and
X = F, CF 3
Solvolysis of Electron-Deficient Norbornyl Triflates
The well-known solvolysis of endo- and exo-2-norbornyl triflates 1 produces exclusively exo-derivatives 2. To establish the influence of electron-withdrawing
groups on the mechanism of the reaction, the solvolysis of endo- and exonorbornyl triflates 3 and 4 has been studied (Scheme 9.1).
Comment and discuss all the following experimental data, proposing a mechanism that could explain the structure of the products obtained in each case.
X
X
X
H
OTf
X
X
X
X
OTf
H
X
OR
H
3
1
X = F, CF 3
2
3
5
6
4
2 R = H, alkyl, COalkyl
solvolysis
4
1
7
Scheme 9.1
Solvolysis of Electron-Deficient Norbornyl
Triflates
Key point: Reaction Intermediates: Carbocations
X
X
H
OTf
X
X
X
X
X
f
OTf
H
X
solvolysis of
and
X = F, CF 3
Solvolysis of Electron-Deficient Norbornyl Triflates
The well-known solvolysis of endo- and exo-2-norbornyl triflates 1 produces exclusively exo-derivatives 2. To establish the influence of electron-withdrawing
groups on the mechanism of the reaction, the solvolysis of endo- and exonorbornyl triflates 3 and 4 has been studied (Scheme 9.1).
Comment and discuss all the following experimental data, proposing a mechanism that could explain the structure of the products obtained in each case.
X
X
X
H
OTf
X
X
X
X
OTf
H
X
OR
H
3
1
X = F, CF 3
2
3
5
6
4
2 R = H, alkyl, COalkyl
solvolysis
4
1
7
Scheme 9.1