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All these scientists are running out of spins! But don't worry, they can send each other help!

Our authors were so smart they didn't need help to make Molecule 45, but they did need some to make Molecule 49. They got this help from Mello, R.; Fiorentino, M.; Fusco, C.; Curci, R. J. Am. Chem. Soc. 1989, 111, 6749-6757.

Methyl(trifluromethyl)dioxirane (TFDO) is used as a catalyst to oxidize alkane and alkene groups. It generally replaces a hydrogen with an hydroxide (-OH) group or it replaces two hydrogens with a double bond. In alkenes, it forms an epoxide from the double bond.

49

(h=TMDO, Dichloromethane)

Now since scientists always chill together, Mello et al. (1989) helped out these next three groups too.

Annese, C.; D'Accolti, L.; Giambastiani, G.; Mangone, A.; Milella, A.; Tuci, G.; Fusco, C. Eur. JOC. 2014, 8, 1666-1671.

This paper was cited for the method to generate a stock solution of TFDO. The TFDO was then used on the SWCNT, a type of carbon nanotube, to form an epoxide ring. The appropriate segment of the reaction is shown below.

Reference

Perrone, S.; Rosato, F.; Salomone, A.; Troisi, L. Tetrahedron. 2013, 19, 3878-3774.

The paper was used in this article as a basis for trying to build more efficient oxaziridines, which are another kind of oxidizing agent, on account of the success of TFDO over DDO which lacks the trifluoromethyl group. This trifluoromethyl group enhances the TFDO's electrophilic capabilities and allows for more facile formation of an epoxide. Thus, the researchers attempted to improve other existing molecules through the use of the electronegative trifluoromethyl group in place of a more common methyl group.

D'Accolti, L.; Annese, C.; De Riccardis, A.; De Giglio, E.; Cafagna, D.; Fanelli, F.; Fusco, C. Eur JOC. 2012, 24, 4616-4621.

This paper used TFDO with it's parent ketone, 1,1,1-trifluoroacetone as a catalyst, which contributed to instability in the reaction mixture, requiring a solid support for the catalyst. Therefore the catalyst was bound in silica as a support, stabilizing it and allowing for simple filtration of the catalyst and reuse if necessary, although the effectiveness of the silica bound catalyst was shown to be decreased with repeated usage.