Adamantme (1) can be amvuted dimtly into adamantan-1.3.5trio1 (5) and into adamantan-1.3.5.7~tetraosool (6) mu&r remarkably mild conditions by employing an exw of isolated mUby~~yMioxirane (3a) ia sob&m_ This new dioxime speck was fomd to be eve 7,ooO-fold macmctivetbandkuethyldbxime(3b)iapaformiqeadmmtme hy&Jxyb&iClb% THE seieuive oxyiimcti~alization of "unaaivated" C-H bonds of saturated hydrocarbons amtinues to be a subjeu d great topical cot~certt.~ In pattiatlar, methods making it pof&le to adtieve the fundiamlimtia~ of adamantme (1) are relevant. since its derivatives are of interest as energetic materials and pbamacz~~ticair~ However, reagatts that allow the direct, seleuive oxyfunctionalization of this target molecule are scarce. For example, oxygenation by the Gii 4 systems yields adamaotan-24 and adamantanme (detived from further oxidaticm of the secmdaty alcohol), alatg with adamantan-l-d On the other hand. hydroxyiations using ozme,5 peroxy acid~~,~ or Cytodmo~ P-450 models'*7*8 yield adamantan-l-d (2). in moS cases aaxmpained by adam~tan-2-ol (and/or adamantanone) in variable amounts. Just "dry oe.c&&m method# and the new HOF/Me&N oxidizing ~ystem'~*' 1 appear pranisin g as for the polyhydroxylation of 1 at the bridgehead positious exclusively. Recently, we have reported on yet another fmitful approadt to hydrocarbon oxyfimuia&iza~~ this came from the ranakable progress reamied by the dmnktry of dioxiranes.3*12 Indeed, mce it became estabilished that the reauion of camate(HSO~-,pefoxanonosulfatc) withke4cmesga1emteadioximncs.~~ the feat4 of i&&m d a few volatile species, such as mcthyl(tritluoromethyl)dioxirane (3a)15 and dimcthyldioxirane (3b),14*16.17 precipitated an intensive utikaticm af these unique oxidants in synthetic applicatims.*2 Among time, the most mnarkablebdatcappea~tobcthe O-atom insertion into umuivti C-H bonds d alkane~.'~~*'~ Indeed .wehaveanployed3a@kllodioxiane)15toachkve dEcktlytbeknv +mpemtumoxyfuncfionalixatkafava&ycfsaturaW hydmcwbonal W& adamantme (1). the higbat rcgiosektivity for tertiary over seamlary C-H oxyiimczionalizatioa was reanded &t > 250). so that -with 1 and 3a ia @molar amounts -adamantan-(2) was Le atly readim produa.'