Face Selectivity of the <i>Diels</i>‐<i>Alder</i> Reaction of 5,6‐Bis((D)methylidene)‐2‐bicyclo[2.2.2]octene

Avenati, Macro; Vogel, Pierre

doi:10.1002/hlca.19830660427

Cited by 14 publications

(3 citation statements)

References 76 publications

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“…The cycloaddition of triene 11 to maleic anhydride has already been discussed in detail [23]. It furnishes a 3:2 mixture of adducts 12 and 13; 12 was obtained pure by fractional recrystallization.…”

Section: Discussionmentioning

confidence: 99%

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The Non‐planarity of the Bicyclo[2.2.1]hept‐2‐ene Double bond. Crystal Structures of Bicyclo[2.2.2]oct‐2‐ene, Bicyclo[2.2.1]hept‐2‐ene, and Bicyclo[2.1.1]hex‐2‐ene Systems

Pinkerton¹,

Schwarzenbach²,

Birbaum

et al. 1984

Helvetica Chimica Acta

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SummaryThe crystal structures of (1 R,4R,5S,8S)-9,l0-dimethylidenetricyclo[6.2.1 .02.7]undec-2(7)-ene-4,5-dicarboxylic anhydride (3), (1 R,4R,5S,8S)-1 1-isopropylidene-9,lO-dimethylidenetricyclo(6.2.1 .02~7]undec-2(7)-ene-4,5-dicarboxylic anhydride (6), (1 R,4R,5S,8S)-9,l O-dimethylidenetricyclo[6.2.2.O2~7]dodec-2(7)-ene-4,5-dicarboxylic anhydride (9), (1R,4R,5S,8S)-tricyclo[6.2.2.02~7]dodeca-2(7), 9-diene-4,5-dicarboxylic anhydride (12) and (4R,SS)-tricyclo[6.1. 1.02~7]dec-2(7)-ene-4,5-dicarboxylic acid (16) were established by X-ray diffraction. The alkyl substituents onto the endocyclic bicyclo[2.2.l]hept-2-ene double bond deviate from the C(1), C(2), C(3), C(4) plane by 13.5" in 3 and by 13.9" in 6, leaning toward the endo-face. No such out-of-plane deformations were observed with the bicyclo[2.2.2]oct-2-ene derivatives 9 and 12. The exocyclic s-cis-butadiene moieties in 3, 6 and 9 do not deviate significantly from planarity. The deviation from planarity of the double bond in bicycl0[2.2.l]hept-Zene derivatives and planarity in bicyclo[2.2.2]oct-2-ene analogues is shown to be general by analysis of all known structures in the Cambridge Crystdographic Data File. The non-planarity of the bicycl0[2.2.l]hept-2-ene double bond cannot be attributed only to bond-angle deformations which would favour rehybridization of the olefinic C-atoms since the double bond in the more strained bicyclo[2.l.l]hex-2-ene derivative 16 deviates from planarity by less than 4".

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Section: Discussionmentioning

confidence: 99%

“…UV (dioxane): 239 (sh, 11 SOO), 246 (1 1 SOO),253 (sh,9 600). IR (KBr) : 2990,2940, 2860, 1850, 1770, 1440, 1240, 1020, 950. (24), 202 (14),195 (25),194 (IS),193 (52),187 (19), 179 (28), 167 (27), 165 (33), 157 (SO), 141 (39, 128 (33), 115 (43), 91 (26), 77 (23). Anal.…”

Section: Experimental Partmentioning

confidence: 99%

The Non‐planarity of the Bicyclo[2.2.1]hept‐2‐ene Double bond. Crystal Structures of Bicyclo[2.2.2]oct‐2‐ene, Bicyclo[2.2.1]hept‐2‐ene, and Bicyclo[2.1.1]hex‐2‐ene Systems

Pinkerton¹,

Schwarzenbach²,

Birbaum

et al. 1984

Helvetica Chimica Acta

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“…Electrophilic additions to 2-methylenenornornene are still known to show the pre-dominant exo selectivity due to the fact that C2 carbon is part of the norbornane ring. The Diels−Alder reactions toward isodicyclopentadiene, showing the bottom-face selectivity with a variety of dienophiles, are interesting exceptions in which the new bond forms on the sp 2 carbons next to the C2 and C3 sp 2 carbons of the norbornane ring . For these reactions, as the olefinic ends are still within the strained norbornane ring, the selectivity is explained by the out-of-plane bending of groups at C2 and C3 on the ring, although it appears that the steric bulkiness of the dienophile also affects the selectivity .…”

Section: Introductionmentioning

confidence: 99%

Remote Exo/Endo Selectivity in Selective Monohydrolysis of Dialkyl Bicyclo[2.2.1]heptane-2,3-dicarboxylate Derivatives

et al. 2010

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High exo-facial selectivity was observed in the selective monohydrolysis of a series of near-symmetric diesters that possess an exo-ester group and an endo-ester group attached on a norbornane or norbornene skeleton. The selectivities were found to be clear-cut, although the reaction center in these reactions is one covalent bond distant from the norbornane or norbornene ring, where the difference of the environment between the exo face and endo face is therefore expected to be negligible. The effect of the co-solvent we studied earlier for the selective monohydrolysis reaction was also confirmed and contributed to improvement of the yields of the half-esters.

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ChemInform Abstract: INTERACTION BETWEEN NONCONJUGATED CHROMOPHORES. PART 20. FACE SELECTIVITY IN THE DIELS‐ALDER REACTION OF 5,6‐BIS((D)METHYLIDENE)‐2‐BICYCLO(2.2.2)OCTENE

Avenati¹,

Vogel²

1984

Chemischer Informationsdienst

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Face Selectivity of the Diels‐Alder Reaction of 5,6‐Bis((D)methylidene)‐2‐bicyclo[2.2.2]octene

Cited by 14 publications

References 76 publications

The Non‐planarity of the Bicyclo[2.2.1]hept‐2‐ene Double bond. Crystal Structures of Bicyclo[2.2.2]oct‐2‐ene, Bicyclo[2.2.1]hept‐2‐ene, and Bicyclo[2.1.1]hex‐2‐ene Systems

The Non‐planarity of the Bicyclo[2.2.1]hept‐2‐ene Double bond. Crystal Structures of Bicyclo[2.2.2]oct‐2‐ene, Bicyclo[2.2.1]hept‐2‐ene, and Bicyclo[2.1.1]hex‐2‐ene Systems

Remote Exo/Endo Selectivity in Selective Monohydrolysis of Dialkyl Bicyclo[2.2.1]heptane-2,3-dicarboxylate Derivatives

ChemInform Abstract: INTERACTION BETWEEN NONCONJUGATED CHROMOPHORES. PART 20. FACE SELECTIVITY IN THE DIELS‐ALDER REACTION OF 5,6‐BIS((D)METHYLIDENE)‐2‐BICYCLO(2.2.2)OCTENE

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