Electronic effects of conjugated enones on their reactivity in transformations of ADDN type

Quantum chemical investigation of structure and stability conformers (R)‐4‐menthen‐3‐one

“…The features of the conformational structure are confirmed by the nuclear magnetic resonance (NMR) spectra H 1 and C 13,15,51 according to which the inversion of the cycle in the (R)-4-menthen-3-one is difficult because the signals of conformers 1b and 1d are absent in the spectra. 52 It is obvious that the predominant attack of one of the sides of the multiple bond during the nucleophilic addition reaction in (R)-4-menthen-3-one is associated with steric repulsion, which results from the peculiarities of the conformational structure.…”

“…The features of the conformational structure are confirmed by the nuclear magnetic resonance (NMR) spectra H 1 and C 13, 15,51 according to which the inversion of the cycle in the (R)‐4‐menthen‐3‐one is difficult because the signals of conformers 1b and 1d are absent in the spectra 52…”

“…In the course of studies of the reactivity of (R)‐4‐menthen‐3‐one, 15 we have shown that this compound has a reactivity uncharacteristic of ordinary enone systems 16 . We have shown that the 1,4‐addition of organometallic compounds and restoration of C = O proceeds with a high stereoselectivity 17 .…”

“…We earlier investigated chemical properties of ( R )‐4‐menthen‐3‐one ( 1 ) obtained from l ‐menthol 4 . We have shown that the chemical properties of 1 are different from the chemical properties other monoterpenoids 10,15,19,23–29 …”

“…[7][8][9][10][11][12][13] Of all the monoterpenoids used, it is (R)-4-menthen-3-one (1) that has the most convenient structure for subsequent transformations and can be easily obtained on the basis of l-menthol 4 extracted from mint oil. 14 In the course of studies of the reactivity of (R)-4menthen-3-one, 15 we have shown that this compound has a reactivity uncharacteristic of ordinary enone systems. 16 We have shown that the 1,4-addition of organometallic compounds and restoration of C = O proceeds with a high stereoselectivity.…”