19870-49-6Relevant articles and documents
Synthesis of S-(+)-methoprene
Odinokov, V. N.,Ishmuratov, G. Yu.,Kharisov, R. Ya.,Serebryakov, E. P.,Tolstikov, G. A.
, p. 98 - 99 (1993)
An optically active juvenile hormone analogue, S-(+)-methoprene (1), is synthesized in six steps from technical grade S-(+)-3,7-dimethyl-1,6-octadiene (''(+)-dihydromyrcene'', e.e. ca. 50percent) by a novel procedure which begins with selective hydroalumination-oxidation to give S-(-)-citronellol.This alcohol is oxidized to give S-(-)-citronellal which on reaction with allylmagnesium chloride affords 6S,10-dimethyl-1,9-undecadien-4R/S-ol (5).Smidt-Moiseev oxygenation of 5 followed by dehydration leads to 6S,10-dimethyl-3E,9-undecadien-2-one.The latter on treatment with isopropoxyethynylmagnesium bromide is transformed into isopropyl 3,7S,11-trimethyl-2E/Z,4E,10-dodecatrienoate which upon Brown solvomercuration-reduction in MeOH gives 1 in 14percent overall yield.
Selective Synthesis of Unsymmetrical Aliphatic Acyloins through Oxidation of Iridium Enolates
Sanz-Marco, Amparo,Martinez-Erro, Samuel,Martín-Matute, Belén
supporting information, p. 11564 - 11567 (2018/07/31)
The first method to access unsymmetrical aliphatic acyloins is presented. The method relies on a fast 1,3-hydride shift mediated by an IrIII complex in allylic alcohols followed by oxidation with TEMPO+. The direct conversion of allylic alcohols into acyloins is achieved in a one-pot procedure. Further functionalization of the Cα′ of the α-amino-oxylated ketone products gives access to highly functionalized unsymmetrical aliphatic ketones, which further highlights the utility of this transformation.
Photochemical transformations of terpenoids in the presence of cyclodextrins
Luzina,Tatarova,Korchagina,Salakhutdinov,Barkhash
, p. 183 - 193 (2007/10/03)
The effect of complexation of terpene compounds with cyclodextrins on photolysis depends on the type of cyclodextrin and on the structure of the initial substrates. In some cases, only a change in the reaction rate is observed; in other cases, the complexation results in allylic rearrangements, hydride and acyl shifts, and cyclization with the formation of four-, five-, and six-membered cycles, whereas only cis-trans isomerization reactions are observed in the absence of complexation.