Ozonolytic Transformations of (R)-4-Menthene-3-One and Its Derivatives in Direction to Low Molecular Weight Bioregulators

Abstract

The author’s data on ozonolytic decyclization (ring opening) of (R)-4- menthene-3-one and its alkylated analogues and application of non-peroxide ozonolysis products in the synthesis of optically active low molecular weight bioregulators including the insects pheromones and juvenoids were generalized. The results of comparative reactivity of the mentioned above mono-terpenoid in the set of α, β-unsaturated cyclic enones were represented.

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 …”

“…Due to the peculiarities of the structure of pheromones in developing convenient ways of their synthesis, the starting compound is of great importance, which should be polyfunctional and contain an optically active center remote from the reaction groups. It has been shown that monoterpenoids such as (R)‐4‐menthen‐3‐one ( 1 ), 4 R‐(−)‐сarvone ( 2 ) 5 and (R)‐(+)‐pulegone ( 3 ) 6 (Figure 1) meet the specified criteria and were successfully used for the synthesis of a wide variety of pheromones 7–13 . 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…”

“…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 …”

“…4 We have shown that the chemical properties of 1 are different from the chemical properties other monoterpenoids. 10,15,19,[23][24][25][26][27][28][29] 2 | COMPUTATIONAL DETAILS Quantum chemical computations were carried out using the "Firefly 8.1.1" 30 software. Final structures of all model alkenes are calculated using the consecutive approach.…”

“…It has been shown that monoterpenoids such as (R)-4-menthen-3-one (1), 4 R-(−)-сarvone (2) 5 and (R)-(+)-pulegone (3) 6 (Figure 1) meet the specified criteria and were successfully used for the synthesis of a wide variety of pheromones. [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.…”