57092-32-7Relevant academic research and scientific papers
Synthesis of 12-Methyl-13-tridecanolide
Stanchev, Stephan,Hesse, Manfred
, p. 1389 - 1392 (1987)
The title compound was prepared from 2-nitrocyclodecanone (2).Compound 2 was treated with 2-methylpropenal to give the Michael-addition product 3 which was reduced to the alcohol 5 and the latter ring-enlarged with Bu4NF to 12-methyl-10-nitro-13-tridecanolide (6) followed by reductive elimination of the NO2 group by Bu3SnH.
Orthocarbonsaeure-ester mit 2,4,10-Trioxaadamantanstruktur als Carboxylschutzgruppe; Verwendung zur Synthese von substituierten Carbonsaeuren mit Hilfe von Grignard-Reagenzien
Voss, Gundula,Gerlach, Hans
, p. 2294 - 2307 (2007/10/02)
The surprising stability of 2,4,10-trioxa-3-adamantyl derivatives 1 against nucleophilic substitution by organomagnesium compounds is discussed and shown to be caused by unfavourable stereoelectronic and steric factors governing the substitution of these cage compounds (Scheme 2).As a consequence, a number of Grignard reagents 2 containing the carboxyl group masked as 2,4,10-trioxa-3-adamantyl group could be prepared and have been reacted in a second step with various electrophiles (cf.Scheme 4).In the products 7-13 and 15b the carboxyl masking group is removed by mild ac id hydrolysis and saponification (cf.Scheme 3) to yield the corresponding acids 16a-21a, 22, and 23a.Acids 21a and 23a have been further transformed to give the macrocyclic lactones 24 and 26, isolated from Galbanum oleo-gum-resin, and acid 22 to give 12-methyl-13-tridecanolide (25), isolated from Angelica root oil.In addition 1-bromo-ω-(2,4,10-trioxa-3-adamantyl)alkanes 1c and 1b have been used to synthesize (+/-)-methyl recifeiolate (29b) and pure cis-ambrettolic acid ((Z)-32a).
