Natural cyclic α, β-enone monoterpenoids in nucleophilic addition reactions

Abstract

The literature on transformations of natural cyclic α,β-enone monoterpenoids into compounds of more complicated structure via 1,2-and 1,4-addition reactions was reviewed. The data were systematized according to the effects of the conditions and nature of the starting substrates on the selectivity of the 1,2-and 1,4-addition reactions.

Influence of electronic structure of (R)-4-menten-3-one on its restricted rotation and inversion

“…This fact followed from experimental found increase of stereoselectivity of 1,4-nuclophilic addition to (R)-4-menthen-3-one with temperature growing [4][5][6]. Taking into account this interesting facts we believe (R)-4-menthen-3-one is not only useful and important compound for the synthesis of a wide range of pheromones [7][8][9][10][11][12][13][14][15][16][17][18][19] and chiral synthons [8,12,20], but interesting object, which can help to investigate correlation between electronic structure and internal rotation and inversion.…”

Synthesis of γ-Aryl Medium-Sized Cyclic Enones by a Domino 4π-Electrocyclic Reaction/Heck–Matsuda Arylation Sequence at Ambient Temperature

“…Cyclic ,-unsaturated ketones are important frameworks found in many biologically active compounds, naturally occurring substances, and versatile intermediates used to synthesize these molecules. 2 Indeed, the syntheses of functionalized ,-unsaturated ketones have been extensively explored, with several approaches developed for introducing alkyl, 3 aryl, 4 or heteroatom-containing groups, 5 especially at the -positions of cyclic enones or 1-siloxy-1,3-dienes as their equivalents (Scheme 1). Whereas the syntheses of -functionalized five-to-seven-membered cyclic enones have been broadly covered in the literature, synthetic methods for medium-sized ones (eight-to ten-membered rings) have rarely been reported, despite their potential utility.…”