Hj. Shine et W. Yueh, REACTIONS OF THIANTHRENE CATION-RADICAL WITH ACYCLIC AND CYCLIC ALCOHOLS, Journal of organic chemistry, 59(13), 1994, pp. 3553-3559
Thianthrene cation radical perchlorate (Th(ClO4-)-Cl-+) reacted readi
ly with cycloalkanols (C-5, C-7, C-8, and C-12), alkan-2-ols (C-3, C-5
, C-6, and C-8), 3-hexanol, neopentyl alcohol, a number of benzyl alco
hols, dl- and (S)-1-phenylethanol, cyclopentyl- and cyclohexylmethanol
s, the exo- and endo-borneols, and norborneols. Reactions were carried
out with an excess of the alcohol in acetonitrile solution containing
2,6-di-tert-butyl-4-methylpyridine. Products were alkenes, ethers, an
d N-substituted acetamides, depending on the structure of the alcohol.
Thianthrene(Th) and its 5-oxide (ThO) were formed in equal amounts. T
he sum of amounts of products from the alcohol was equal to the amount
of ThO. All reactions are interpretable on the basis of the ultimate
formation and further reactions of a 5-alkoxythianthreniumyl ion (ROTh
(+)). The predominant formation of nortricyclene from the norborneols
is striking and is discussed. Swern-Moffatt-type oxidations of the alc
ohols were not observed.