The transannular electrophilic reaction of alkenyl nitroso compounds and the stereochemistry of nitrosyl chloride addition

Abstract

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...

Preparations ofC-Nitroso Compounds

“…Similar considerations have been applied to the reaction products of nitrosyl chloride and 1,5-cyclooctadiene and trans,trans,trans- cyclododecatriene . Ponder and Wheat studied the dimeric nitrosochloride products of the addition to the strained bicyclic olefins norbornene, norbornadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, and bicyclo[2,2,2]octene-2.…”

“…Similar considerations have been applied to the reaction products of nitrosyl chloride and 1,5-cyclooctadiene and trans,trans,trans-cyclododecatriene. 97 Ponder and Wheat 98 studied the dimeric nitrosochloride products of the addition to the strained bicyclic olefins norbornene, norbornadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, and bicyclo[2,2,2]octene-2. Other authors have given careful consideration to the stereochemistry of nitrosyl chloride addition products to various terpenes, e.g., γ-terpinene, 99 sylvestrene, 100 p-menth-1-ene, limonene and R-pinene, 101 (()-R-terpinyl acetate, 102 (+)-car-3-ene, 103 and transβ-terpineol.…”

Nitrosyl chloride addition to cycloalkenyltrimethylsilanes. An unexpected reversal of regiochemistry of addition, and synthesis of β-aminosilanes

“…The α-chlorooxime can eventually be hydrolyzed to α-chloroketone 4 or used in other ways. 3 The NOCl addition to alkene is shown to be trans 1-3 as well as cis, 5,6 and usually follows…”

Photochemistry of nitro and nitroso compounds

“…(96) 216 Yuan L. Chow product, bianthrone. However, the observation that phenols are formed only in 'undried' benzene, and not in anhydrous benzene (equation 97)50, suggests that the thermally o r photolytically initiated hydrolysis of the corresponding nitrite may be the more probable pathway under the conditions.…”

“…A poor yield of 218 is also obtained in the photolysis of 215 in ether. It appears that the pathways to 216 the nitro group is transmitted to the epoxide ring, causing ionization of a C-0 bond followed by a nitro group shift or HNO2 elimination. The competing pathway is hydrogen abstraction by the excited nitro group leading to a variety of reduction stages; at a certain stage the epoxide ring may be opened with the aid of electronic interactions or by another photoexcitation.…”