121950-27-4Relevant articles and documents
Catalytic Hydrothiolation: Counterion-Controlled Regioselectivity
Yang, Xiao-Hui,Davison, Ryan T.,Nie, Shao-Zhen,Cruz, Faben A.,McGinnis, Tristan M.,Dong, Vy M.
, p. 3006 - 3013 (2019)
In this Article, we expand upon the catalytic hydrothiolation of 1,3-dienes to afford either allylic or homoallylic sulfides with high regiocontrol. Mechanistic studies support a pathway in which regioselectivity is dictated by the choice of counterion associated with the Rh center. Non-coordinating counterions, such as SbF6-, allow for η4-diene coordination to Rh complexes and result in allylic sulfides. In contrast, coordinating counterions, such as Cl-, favor neutral Rh complexes in which the diene binds η2 to afford homoallylic sulfides. We propose mechanisms that rationalize a fractional dependence on thiol for the 1,2-Markovnikov hydrothiolation while accounting for an inverse dependence on thiol in the 3,4-anti-Markovnikov pathway. Through the hydrothiolation of an essential oil (β-farnesene), we achieve the first enantioselective synthesis of (-)-agelasidine A.
SYNTHESIS WITH MANGANIC SALTS; PART III: SYNTHESIS OF 1,4-DIKETONES THROUGH MANGANIC ACETATE-MEDIATED ADDITION OF KETONE TO ISOPENTENYL SULFONES. ACETOXYLATION OF Β,Γ-UNSATURATED KETONES BY MANGANOUS AND CUPRIC ACETATES
Breuilles, Pascal,Uguen, Daniel
, p. 705 - 720 (2007/10/02)
Conditions have been found to selectively add ketones to isopentenyl sulfones.The major product, a ketone bearing a methylene group at the γ position, gave upon ozonolysis the corresponding 1,4-diketone.The usefulness of the overall process was illustrated by the efficient syntheses of jasmone and of one half of pyrenophorine.The γ-acetoxy conjugated enones that invariably formed during these additions resulted from the oxidation of an isomeric β,γ-unsaturated ketone by manganous and cupric acetates.Such an acetoxylation has been used to prepare 6β-acetoxy-cholestenone from cholesterol and also to prepare chrysanthemic acid.
