Enantioselective Total Synthesis of Eudesma-3,11(13)-dien-12-oic Acid

Abstract

The first enantioselective total synthesis of eudesma-3,11(13)-dien-12-oic acid 1 was achieved starting from (+)-dihydrocarvone in ten steps.

Catalytic Allylic Chlorination of Natural Terpenic Olefins Using Supported and Nonsupported Lewis Acid Catalysts

“…Among the versatile natural products bearing these groups, terpenes represent a sustainable supply of intermediates for several functionalization segments of the fine chemical industry, for example, the manufacture of flavors and fragrances [6][7][8]. Allylic chlorination represents a convenient way to functionalize terpenes bearing an allyl, vinyl, or isopropenyl group since further manipulation on the chloride may lead to several functional groups for the synthesis of natural products [9][10][11][12][13]. Previously, we have reported the allylic substitution of optically active natural terpenic allylic chloride derivatives in good yields [14,15].…”

InCl3/NaClO: A reagent for allylic chlorination of terminal olefins

“…A feasible procedure for this purpose was reported by Wolinsky and co-workers, using solid CO 2 and calcium hypochlorite. 14,15 As an alternative, Li and co-workers employed a combination of the Vilsmeier reagent and H 2 O 2 in the synthesis of eudesmane acids, but the presence of POCl 3 excludes the use of acid-sensitive substrates. 16 Recently, Massanet and co-workers, described the preparation of allylic chlorides by reaction of terminal olefins with sodium hypochlorite in the presence of cerium trichloride heptahydrate as an ene-type reaction.…”

“…[1][2][3][4][5][6] These compounds are usually prepared from the corresponding allylic alcohols by the action of a variety of reagents, such as hydrochloric acid, 7 thionyl chloride, 8 titanium (IV) chloride, 9 N-chlorosuccinimide, 10 methanesulfonyl chloride/lithium chloride, 11 or chloromethylsilanes. 12 Allylic chlorination is a convenient alternative method of terminal olefin functionalization.…”