The Effects of Homoconjugated Cyclopropane and Oxirane Rings on the <i>Diels‐Alder</i> Reactivity of 2,3‐bis (methylidene)norbornane

Pilet, Olivier; Chollet, André; Vogel, Pierre

doi:10.1002/hlca.19790620731

Cited by 22 publications

(2 citation statements)

References 60 publications

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“…The major isomer 13 was isolated pure in 59% yield after two recrystallizations. Photooxidation (02, visible light, meso-te- ') For kinetic data on this cycloaddition, see [19].…”

Section: (€)-4mentioning

confidence: 99%

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Face Selectivity in the Diels‐Alder Additions and Chelotropic Addition of Sulfur Dioxide to 2‐(D)Methylidene‐3‐methylidenebicyclo[2.2.1]heptane

Carrupt

Berchier

Vogel

1985

Helvetica Chimica Acta

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The stereoselectivity of the cycloadditions of 2-(D)methylidene-3-methylidenebicyclo[2.2. llheptane (4) to various dienophiles has been determined. The exo-us. endo-face selectivity depends on the type of dienophiles, and for olefinic ones, on the mode of attack (Alder-us. anti-Alder endo rule). It is > 9:1 with N-phenyltriazolinedione (NPTAD) and ethylenetetracarbonitrile (TCNE), < 1 :9 with dimethyl acetylenedicarboxylate (DMAD), 30 f 5:70 i 5 with DMAD in the presence of AICl,, 15 f 5:85 f 5 with dehydrobenzene and 40 f S:60 f 5 with ' 0 2 generated photochemically ( Table I ) . With para-benzoquinone and maleic anhydride, the exo-us. endo-face selectivity is < 1.9 and 20 f 5:80 f 5, respectively, for their anti-Alder mode of attack; it is 50 i 5:50 f. 5 and 55 f 5 :45 * 5, respectively, for their Alder mode of reaction. Under conditions of kinetic control, the chelotropic addition of SO, to 4 is endo-face selective.Face selectivity can be observed for reactions of a n-function attached to a skeleton which is not symmetrical with respect to the 'n-plane' of this function [l] [2]. The face selectivity of the Diels-Alder additions of isodicyclopentadiene ( = 4,5,6,7-tetrahydro-4,7-methano-2H-indene; 1 was first studied by Alder and coworkers . A large variety of dienophiles were found to add to 1 preferentially onto its endo face. This was attributed by Paquette and Gleiter [5] to a kinetic stereoelectronic factor. According to these authors, the norbornane skeleton causes mixing of and II orbitals of the diene moiety such that the symmetrical subHOMO (n,) of the diene of 1 tilts its terminal p orbitals inward in the exo face of the norbornane moiety, and outward in the endo face. When a dienophile approaching from the endo face closed-shell repulsion between the dienophile HOMO and the tilted n, orbital of the diene is avoided. These two orbitals would overlap more in a exo -face attack.Bartlett et al. [7] reported, however, that the face selectivity for the cycloadditions of maleic anhydride to 1 can be reversed by changing the solvent. Later, Paquette et a/. [6] found that the Diels-Alder addition of N-methyltriazolinedione (NMTAD) and Nphenyltriazolinedione (NPTAD) to 1 were highly exo -face selective whereas those to the didehydro analog 2 were endo -face selective.

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“…The major isomer 13 was isolated pure in 59% yield after two recrystallizations. Photooxidation (02, visible light, meso-te- ') For kinetic data on this cycloaddition, see [19].…”

Section: (€)-4mentioning

confidence: 99%

“…') For kinetic data on this cycloaddition, see [19]. traphenylporphine, CH,Cl,, 20°C) of 3 has been reported to yield the endoperoxide 15 [22].…”

Section: ")mentioning

confidence: 99%

Face Selectivity in the Diels‐Alder Additions and Chelotropic Addition of Sulfur Dioxide to 2‐(D)Methylidene‐3‐methylidenebicyclo[2.2.1]heptane

Carrupt

Berchier

Vogel

1985

Helvetica Chimica Acta

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[4 + 2]‐Cycloaddition of Singlet Oxygen and Phenyltriazolinedione with Bicyclo[6.1.0]nona‐2,4,6‐triene and Derivatives

1982

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The dienic reactivity of the bicyclononatrienes l a ([4.3.0]-isomer) and 1 b ([6.1 .O]-isomer) and its oxa-derivative 6 (cyclooctatetraene epoxide) as well as 1,3,5-cyclooctatrienone (7), towards singlet oxygen ('0,) and phenyl-l,2,4-triazoline-3,5-dione (PTAD) as dienophiles has been investigated. Except for l a , which affords the endoperoxide 9a in 60% yield, the remaining substrates l b , 6 , and 7 do not react with '0,. With PTAD l a , l b , 6 , and 7 afford the urazoles 10a, 8b, 1212, and 11, respectively. Unusual is the fact that the bicyclo[6. products 2 a -c (Eq. 1). The valence isomer l b has been prepared some time ago'); its dienic reactivity has been investigated to some extent. For example, it was reported2a-c) that tetracyanoethylene gave the [2 + 21-cycloadduct 3 and the [4 + 21-cycloadduct 3c, while maleic anhydride afforded a mixture of the products 4a and 4c in 33% and 67%, respectively. Clearly, the [4 + 21-cycloadduct 4a must be derived from the valence isomer l a and the [4 + 21-cycloadducts 3c and 4c from l c in order to rationalize these results. Other dienophiles that have been employed include dimethyl acetyienedicarboxylatezd), chlorosulfonylisocyanateZe), and

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Bicyclofulvene, IX. Stereoelektronische Effekte bei der Addition an 8‐Methylentricyclo[3.2.0 ^2,4 ]octan‐Derivate

1983

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Das Aziridin-Derivat 9 wird bei der Dichlorcarben-Addition, der Hydroborierung und der Hydrierung etwas mehr von der syn-als von der anti-Seite her angegriffen. Wahrend bei 9 keine nennenswerte Wechselwirkung zwischen Dreiring und semicyclischer Doppelbindung besteht, laBt sich eine deutliche Orbital-Wechselwirkung bei den Cyclopropan-Derivaten 6 und 7 nachweisen. Dies wird mit einem bevorzugten anti-Angriff der genannten Reagenzien auf die Doppelbindung in 6 und 7 in Zusammenhang gebracht. Bicyclofulvenes, IX Stereoelectronic Effects in Additions to 8-Methylenetricycl0[3.2.1.O~~~]octane DerivativesAddition of dichlorocarbene to the double bond of the aziridine derivative 9 as well as hydroboration or hydrogenation proceed with a slight syn preference. Whereas 9 lacks significant interaction between the three-membered ring and the semicyclic double bond, interaction is marked in the cyclopropane derivatives 6 and 7. This is considered to cause the preferred anti-attack by the above mentioned reagents.Oberseite und Unterseite einer Doppelbindung sind nur bei solchen Olefinen gleich, in denen die Ebene der Doppelbindung eine Symmetrieebene des Molekiils ist, wie z. B. bei 1. Bei anderen Olefinen kann die Storung, die zu einer Ungleichheit der Ober-und Unterseite fiihrt, sterische und elektronische Ursachen haben: So liegt z. B. in 2') eine einseitige elektronische und sterische Wechselwirkung vor.DaL3 die Doppelbindung in 2 von Elektrophilen anti zum Aryl-Rest angegriffen wird, ergibt sich damit allein schon aus sterischen Griinden. Um den EinfluD elektro-

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The Effects of Homoconjugated Cyclopropane and Oxirane Rings on the Diels‐Alder Reactivity of 2,3‐bis (methylidene)norbornane

Cited by 22 publications

References 60 publications

Face Selectivity in the Diels‐Alder Additions and Chelotropic Addition of Sulfur Dioxide to 2‐(D)Methylidene‐3‐methylidenebicyclo[2.2.1]heptane

Face Selectivity in the Diels‐Alder Additions and Chelotropic Addition of Sulfur Dioxide to 2‐(D)Methylidene‐3‐methylidenebicyclo[2.2.1]heptane

[4 + 2]‐Cycloaddition of Singlet Oxygen and Phenyltriazolinedione with Bicyclo[6.1.0]nona‐2,4,6‐triene and Derivatives

Bicyclofulvene, IX. Stereoelektronische Effekte bei der Addition an 8‐Methylentricyclo[3.2.0 ^2,4 ]octan‐Derivate

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The Effects of Homoconjugated Cyclopropane and Oxirane Rings on the Diels‐Alder Reactivity of 2,3‐bis (methylidene)norbornane

Cited by 22 publications

References 60 publications

Face Selectivity in the Diels‐Alder Additions and Chelotropic Addition of Sulfur Dioxide to 2‐(D)Methylidene‐3‐methylidenebicyclo[2.2.1]heptane

Face Selectivity in the Diels‐Alder Additions and Chelotropic Addition of Sulfur Dioxide to 2‐(D)Methylidene‐3‐methylidenebicyclo[2.2.1]heptane

[4 + 2]‐Cycloaddition of Singlet Oxygen and Phenyltriazolinedione with Bicyclo[6.1.0]nona‐2,4,6‐triene and Derivatives

Bicyclofulvene, IX. Stereoelektronische Effekte bei der Addition an 8‐Methylentricyclo[3.2.0 2,4 ]octan‐Derivate

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Bicyclofulvene, IX. Stereoelektronische Effekte bei der Addition an 8‐Methylentricyclo[3.2.0 ^2,4 ]octan‐Derivate