960121-25-9

Upstream product

• 994-30-9 triethylsilyl chloride 
• 229323-96-0 1,1-dihydroperoxy-(4-tert-butyl)cyclohexane 
• 98-53-3 4-tercbutyl-cyclohexanone 
• 79271-56-0 triethylsilyl trifluoromethyl sulfonate 

Downstream Products

• 1101829-30-4 C₂₂H₃₄O₃ 
• 869298-33-9 benzhydryl-(8-tert-butyl-1,2-dioxaspiro[4.5]dec-3-ylmethyl)-dimethylsilane 

Relevant academic research and scientific papers

Probing the Peroxycarbenium [3+2] Cycloaddition Reactions with 1,2-Disubstituted Ethylenes: Results and Insights

The causes for the title reaction to be limited to only the alkenes with an unsubstituted terminal alkenic carbon were explored. In some “failed” cases the cycloaddition products actually formed but rearranged concurrently. An oxygen atom or a N-Boc (Boc=

Generation of singlet oxygen from fragmentation of monoactivated 1,1-dihydroperoxides

The first singlet excited state of molecular oxygen (1O 2) is an important oxidant in chemistry, biology, and medicine. 1O2 is most often generated through photosensitized excitation of ground-state oxygen. 1O2 can also be generated chemically through the decomposition of hydrogen peroxide and other peroxides. However, most of these "dark oxygenations" require water-rich media associated with short 1O2 lifetimes, and there is a need for oxygenations able to be conducted in organic solvents. We now report that monoactivated derivatives of 1,1-dihydroperoxides undergo a previously unobserved fragmentation to generate high yields of singlet molecular oxygen (1O2). The fragmentations, which can be conducted in a variety of organic solvents, require a geminal relationship between a peroxyanion and a peroxide activated toward heterolytic cleavage. The reaction is general for a range of skeletal frameworks and activating groups and, via in situ activation, can be applied directly to 1,1-dihydroperoxides. Our investigation suggests the fragmentation involves rate-limiting formation of a peroxyanion that decomposes via a Grob-like process.

Synthesis of spiro-1,2-dioxolanes and their activity against Plasmodium falciparum

Artemisinin-derived compounds play an integral role in current malaria chemotherapy. Given the virtual certainty of emerging resistance, we have investigated spiro-1,2-dioxolanes as an alternative scaffold. The endoperoxide functionality was generated by the SnCl4-mediated annulation of a bis-silylperoxide and an alkene. The first set of eight analogs gave EC50 values of 50-150 nM against Plasmodium falciparum 3D7 and Dd2 strains, except for the carboxylic acid analog. A second series, synthesized by coupling a spiro-1,2-dioxolane carboxylic acid to four separate amines, afforded the most potent compound (EC50 ～5 nM).

Synthesis of 1,2-dioxolanes by annulation reactions of peroxycarbenium ions with alkenes

(Chemical Equation Presented) The annulation reactions of alkenes with peroxycarbenium ions enable the synthesis of a variety of functionalizable 1,2-dioxolanes. Triethysilyl-protected peroxycarbenium ions proved to be optimal for the annulation reaction. Using this method, plakinic acid analogues can be synthesized in three steps from the corresponding ketone and alkene.