Y C .~ L. CHOW, K , SO\I-\SEKHARA?< PILLAY, and H~R V E RTCITARL). Ca1-l. J. Chem. 57.2913Chem. 57. (1979.Nitrosql chloride reacted with :,5-c:.clooctadiene and trcir!. ~,tr.nrir,trr~i~.~-1,5,9-cyc1od~deca-triene i11 methglene chloride by the c,D-addition to g i~e chioronitroso al!tenes u.iik cis a n 2 thi-eo (tintis) configuraiion, respcctikely. These enantionioiphic C-nitrcso colnpounds were isolated as a single compor~iid for the fornier; and a n i i~t u r e io: the latter, of dl arid (or) inero din?ers, the presence of v,hich \\as readily monitored by 13C nn?r spectroscop). The former can assume a coi~ibrrnaiion to place the rc-bonds of the nitroso and olefinic groups in interacting vicir~ity arld undergo a n acid catalyzed intramolecular electrcphiiic cyciization to give bicyclic hjdroxylanlines mliich are readily air oxidized to the co:r.esponding nitroxide radicals. Rearrangement in acetic a n h~d r i d e -rneihjiene chloride afforded good 5ields of the stable bicyciic h y d r o x~l -ainine acetates s\hich cerved as precursors to generale the corresponding nitrovides under mild ccnditions. Photoaddition of.\ -iiitrosopiperidine to I ,5-cqclooctadiene also partlq afforded the ci\-aniinonirroso adduct 14 hich underuent the intrainolecular addition to gi1.e hydrorylamines. The thrco(ti-at!.\)-.chlmitroso alhenes failed to c)c!izc in simiiar fa5hion under comparable conditions. Nitrosylchloride added cxclusi\ely to the ri.iiir,-double bond of ti.o,i.!,cic-1,s-cqclodecadiene ~i i t h o u t i-egiospecificity biii ,"\as belieicd to foliou !he stereospecific cih-addition; this chioroilitroso coillpoiliid aiso undernent the acid catal>zed :-ransanniilar reaction to give simllar hydrox~lanilr~es :hzr were not isolated in pure states. Chem. 57.1923Chem. 57. (1979.Par une additioil cij, le rhiorure de nitrosq!e dans le chlorure de nitthylene se fixe sur le cyclooctadiene-! ,5 st ie cyclociodCcatriene-1,5,9 ri-iit~.r.f;~ans~~ims pour conduire respectivemefit 2ux alcenes chioroni;roses <,is et ri'zi-ho !irnrr.r). Les coinposis ~iiantiomorphes C-nirrosis sont isoles sous foi me de co~irposd unique dans le cas du cyclooctadiene et sous forme d'un melange de ril et ou de din~eres ii?4so dans le second cas. La presence de ces derniers a ete revklee par l'etude des spectres rmn du 'T. i e s composis derikant du cyclooctadiene--1,s adoptent une con5guration qui place ic5 !iaisons n des gl.oupements nitroso et olefines a u voisinage l'un de I'autre. Ceci pennet alors une cyclisation e!ecti.ophile in(ranio!eculaire, cata!ysCe par l'acide, cici conduit ails h>drou)ismines bicqcliques. Ces derniers s'oxSdent facilemcnt B I'zir en i.adicaax iiiri-oso corxspondants. L a transposition dans un r?C!ange a n h~d r e acQtique --ch1ori.il.e tie r:iCthyIi.re foamit avec de iions rendeiiients Ies acCtates d'h~~droxylaminei bicycliilues ~i z h l e s qui dani 2e.; coi~ditions douces serkent de prec~~rseurs aux nitroxydes corresim~?dants. L'addirion photochiniique de :a N-nitroso pipkridine a u cyc1ooc;adiene-i,5 fo~~:-iiit awsi en parti...