Convenient synthesis of new functionalized cyclopropanes from monoterpenic olefines

Abstract

Five new cyclopropyl-ketoacids were prepared in good yields from monoterpenic olefines using solid-liquid phase transfer catalysis (SL-PTC) dichlorocyclopropanation reaction followed by oxidative cleavage with RuCl 3 -NaIO 4 system. The nonchlorinated cyclopropanes were obtained by sodium/methanol reduction of the corresponding gem-dichlorocyclopropanes.

Recent advances in the syntheses, transformations and applications of 1,1-dihalocyclopropanes

“…gem-Dichlorocyclopropyl derivatives of limonene, terpinolene and γ-terpinene were synthesized using NaOH and benzyltriethyl ammonium chloride (TEBAC) in CHCl 3 at room temperature affording monocyclopropanated products in good yield (Scheme 1). 10 oxirane ring of the resulting product 6 was cleaved oxidatively using the RuCl 3 -NaIO 4 catalytic system; crystallization of the product led to the respective diastereomers of the dihalocyclopropane ring system 7.…”

(5R)-5-[(1R)-2,2-Dichloro-1-methylcyclopropyl]-2-methylcyclohex-2-en-1-one

“…For background to and applications of dichlorocyclopropane derivatives, see: Hirota et al (1996); Kü nzer et al (1996); Ziyat et al (2004);Fedorynski (2003). For the synthesis and structures of optically active dihalogenocylopropanes reported by our group, see: Ziyat et al (2002); Boualy et al (2009); Ziyat et al (2006). For puckering parameters, see: Cremer & Pople (1975).…”

“…These compounds have found wide applications as substrates for the synthesis of many class of compounds such as pyrethroides (Ziyat et al, 2004), benzocyclopropenes or cyclopentadiene derivatives (Fedorynski, 2003), which are not easily obtained using other starting materials. As a part of our ongoing research aimed at the synthesis of optically active dihalogenocylopropanes from terpenes (Ziyat et al, 2002;Ziyat et al, 2004;Boualy et al, 2009;Ziyat et al, 2006), the title compound has been prepared and its crystal structure is reported herein.…”

Green Synthesis of Carvenone by Montmorillonite-Catalyzed Isomerization of 1,2-Limonene Oxide

“…dihydrocarvone [3,4] and 1,2-limonene oxide. Because the latter compound is easily prepared from naturally available limonene [5], the interest for direct syntheses of carvenone from 1,2-limonene oxide has been increasing [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21]. However, most of the related reports showed that the selectivity towards carvenone was not good as expected.…”