Reactions of 3-iodolevoglucosenone with sodium derivatives of some CH acids. Chiral cyclopropanes and stable oxetenes

Abstract

3-1odolevoglucosenone reacts with the sodium derivative of ethyl cyanoacetate at -60 ~ to give a tetrasubstituted eyclopropane derivative; similar reactions of the sodium derivatives of ethyl acetoacetate and acetylacetone at -60 '(2 afford the expected transformed Michael adducts, while at 20 *C, O,C-dialkylated products of the oxetene series are formed.

Levoglucosenone: Bio-Based Platform for Drug Discovery

“…Enantiopure cyclopropanes are found in a variety of existing biologically active molecules, and are favoured for their rigidity and relative stability under biological conditions. There are a number of approaches for the preparation of cyclopropanes from LGO including the direct cyclopropanation of the alkene of either LGO or one of its derivatives ( Samet et al, 2007 ; Ledingham E. et al, 2017 ), reactions of malonates with the 3-iododerivative of LGO ( Valeev et al, 1999 ), or by transformation of LGO into a suitably reactive species for cyclization. Using this last approach, Stockton and Greatrex (2016) converted LGO into substituted butyrolactones via either 1) reductive cross-coupling and Baeyer-Villiger oxidation, or 2) reduction then Baeyer-Villiger oxidation ( Figure 2 ).…”