Aza analogy to singlet oxygen. The simultaneous stereospecific functionalization of the four cyclopentadiene sp2 carbon atoms by reaction with nitrosochloroethylenes

Viehe, H. G.; Merényi, R.; Francotte, Eric; Meerssche, M. Van; Germain, G.; Declercq, J.P.; Bodart-Gilmont, J.

doi:10.1021/ja00449a055

Cited by 43 publications

(13 citation statements)

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“…X-ray study; it is derived from an unstable primary adduct (8) . 17 We found that 2,2-dichloronitrosoethylene also reacts with several other dienes but the adducts proved to be very unstable and we have so far been unable to characterise them. No adduct was obtained with indene.…”

Section: Results and Discussiionmentioning

confidence: 90%

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Cycloaddition reactions of nitrosoalkenes and azoalkenes with cyclopentadiene and other dienes

Faragher¹,

Gilchrist²

1979

J. Chem. Soc., Perkin Trans. 1

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Section: Results and Discussiionmentioning

confidence: 90%

“…The pyridazine ( l l j ) (0.289 g, 1.4 mmol) in methanol (30 cm3) was hydrogenated over Pd-C to give 3-methyl-lphenyl-4,4a, 5,6,7,7a-hexahydro-lH-~yc2openta[c]pyridazine (17) (0.285 g, 98%), m.p. 38 "C (from pentane) (Found: C, 78.7; H , 8.5; N, 13.3.…”

Section: Phenyz-6-a-~nethylvinyz-56-dihydro-4h-mentioning

confidence: 99%

Cycloaddition reactions of nitrosoalkenes and azoalkenes with cyclopentadiene and other dienes

Faragher¹,

Gilchrist²

1979

J. Chem. Soc., Perkin Trans. 1

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“…127 It should be emphasised that the rearrangement to epoxyaziridines is typical only of adducts of halo-substituted nitrosoalkenes with cyclic dienes. Cycloadducts of nitrosoalkenes with acyclic dienes, 8 as well as the products of [4+2]-cycloaddition of cyclic 1,3-dienes to the nitroso groups of other types of nitroso compounds, 121,127 do not undergo this rearrangement. This regularity has not been explained yet.…”

Section: A Nitrosoalkenes As 2p Systems In Cycloaddition Reactionsmentioning

confidence: 99%

Conjugated nitrosoalkenes

Lyapkalo¹,

Ioffe²

1998

Russ. Chem. Rev.

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Published data on the preparation, structure, physical and chemical properties, and reactivity of nitrosoalkenes are described systematically. The influence of the structure and stereoelectronic effects of substituents at the double bond on the stability of nitrosoalkenes is analysed. Primary attention is paid to concerted cycloaddition of nitrosoalkenes to miscellaneous multiple bonds, in particular, to the problems of regio-, stereo-, and enantioselectivity of [4 + 2]-cycloaddition of nitrosoalkenes to alkenes. The bibliography includes 183 references.

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“…The reactions of 1 in methylene chloride with cycloalkadienes were essentially complete in seconds at -78"C, producing the Diels-Alder cycloadducts in high yields (8,9). Earlier, we reported that 1 reacted as a nitrosoformic chloride equivalent in the cyclization with acyclic 1,3-butadienes (9).…”

mentioning

confidence: 94%

Study of trichloronitrosomethane: regioselective cycloadditions of 2-substituted-1,3-butadienes

Lin¹,

Hsu²

1989

Can. J. Chem.

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CHENG-TUNG LIN and WEN-JEI HSU. Can. J. Chern. 67, 2153 (1989). The regioselectivity of cycloaddition reactions of trichloronitrosomethane (1) with 2-alkyl (R = Me, Et, i-Pr, t-Bu, CF3, Bz, and C1) and 2-aryl (Ar = Ph, 4-CH30Ph, 4-CH3Ph, 3-CH3Ph, and 4-ClPh) 1,3-butadienes is described. The orientation of cycloaddition is substituent dependent, producing 2,5-disubstituted (para) and 2,4-disubstituted (meta) 3,6-dihydro-1,2-oxazines from 2-alkyl-and 2-aryl-l,3-butadienes respectively. Increasing the bulk of the substituent from methyl to tert-butyl in 2-alkyl-l,3-butadienes increases the regioselectivity. Kinetic studies in various solvents indicate that plots of log k m / k H vs. Hammett u + values give straight lines with the p values lying between -0.60 and -0.91 for the reactions with 2-aryl-1,3-butadienes. A concerted reaction mechanism is proposed and the orientation preference is consistent with frontier molecular orbital predictions for 2-alkyl-l,3-butadienes. In the reactions with 2-aryl-l,3-butadienes, a transition state leading to a spin-paired diradical, which then converts by partial electron transfer to zwitterionic structure, is proposed. de la cycloaddition depend du substituant; i partir des 2-alkyl-et des 2-aryl-buta-l,3-diknes, on obtient respectivement des 3,6-dihydro-l,2-oxazines disubstitukes en 2,5 (para) et en 2,4 (mtta). Avec les 2-alkyl-buta-l,3-dibnes, une augmentation du volume du substituant (en allant du mkthyle au tert-butyle) provoque une augmentation de la rkgiosklectivitt. Des ttudes cinktiques dans divers solvants suggkrent que les courbes du log k m / k H vs. les valeurs u + de Hammett donnent des droites avec des valeurs de p variant de -0,60 A -0,91 pour les rkactions des 2-aryl-buta-l,3-dibnes. Pour les 2-alkyl-buta-l,3-diknes, on suggkre un mtcanisme rkactionnel concert6 et la prtfkrence de I'orientation est en accord avec les prkdictions des orbitales molkculaires frontikres. Dans les reactions des 2-aryl-buta-l,3-dibnes, on propose une ktat de transition conduisant A un diradical dont les spins sont pairks qui se transforme ensuite en une structure zwitterionique par un transfert partiel d'klectrons.

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Aza analogy to singlet oxygen. The simultaneous stereospecific functionalization of the four cyclopentadiene sp2 carbon atoms by reaction with nitrosochloroethylenes

Abstract: Nitro1 and nitroso2 activated acetylenes and chloroethylenes 1 as their formal hydrochlorides3•4 have been studied in our

Cited by 43 publications

References 1 publication

Cycloaddition reactions of nitrosoalkenes and azoalkenes with cyclopentadiene and other dienes

Cycloaddition reactions of nitrosoalkenes and azoalkenes with cyclopentadiene and other dienes

Conjugated nitrosoalkenes

Study of trichloronitrosomethane: regioselective cycloadditions of 2-substituted-1,3-butadienes

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