Wacker-type oxidation of internal alkenes using Pd(Quinox) and TBHP
The Pd-catalyzed TBHP-mediated Wacker-type oxidation of internal alkenes is reported. The reaction uses 2-(4,5-dihydro-2-oxazolyl)quinoline (Quinox) as ligand and TBHP(aq) as oxidant to deliver single ketone constitutional isomer products in a predictable fashion from electronically biased olefins. This methodology is showcased through its application on an advanced intermediate in the total synthesis of the antimalarial drug artemisinin.
Deluca, Ryan J.,Edwards, Jennifer L.,Steffens, Laura D.,Michel, Brian W.,Qiao, Xiaoxiao,Zhu, Chunyin,Cook, Silas P.,Sigman, Matthew S.
p. 1682 - 1686
(2013/04/10)
INTRAMOLECULAR HYDROSILATION OF ACETYLENES: REGIOSELECTIVE FUNCTIONALIZATION OF HOMOPROPARGYL ALCOHOLS
Platinum-catalyzed intramolecular hydrosilation of hydrodimethylsilyl ethers of homopropargyl alcohols proceeds regioselectively in a 5-exo-dig mode.The resulting vinylsilanes can be transformed into 3-alkanon-1-ol and 3-bromo-3-alken-1-ol derivatives by H2O2 oxidation and bromine cleavage, respectively.