Bicyclo[3.3.1]non-1-ene

Marshall, James A.; Faubl, Hermann

doi:10.1021/ja00999a049

Cited by 46 publications

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“…In a dry box filled with nitrogen, the crude product (0.32 g, 22%) was diluted with pentane, washed with water, dried over NazS04, and distilled in a bulb tube at 80"/12 Torr. 0.238 g (16%) of 1 were obtained as a colourless oil, identical with the product described by Wiseman & Pletcher [7], and Marshall & Fuubl [8] 1 with 2,5-dighenylbenzo[c] Synthesis of bicyclo[3.3.1l-I(2)-nonene ( 1 ) by intramolecular Wittig reaction using other solvents and buses. For detailed procedures see [12].…”

Section: Experimental Partmentioning

confidence: 56%

“…Based on this research, Fawcett drew the conclusion that compounds with a double bond at the bridgehead cannot be isolated if the total number of bridge atoms S2) is less than nine [6]. In 1967, both Wiseman [7] and Marshall [8] reported the successful synthesis of bicyclo[3.3. I]-l(2)-nonene (l), a reactive but stable bridgehead olefin with seven bridge carbon atoms only.…”

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confidence: 99%

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ChemInform Abstract: THE SYNTHESIS OF STRAINED METHYLENE‐BRIDGED BICYCLIC OLEFINS BY THE INTRAMOLECULAR WITTIG REACTION

Becker¹

1977

Chemischer Informationsdienst

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SummaryA convenient synthesis of the strained methylene-bridged trans-cyclooctenes bicyclo[3.3.l]-1(2)-nonene (l), bicyclo[4.2.1]-1(8)-nonene (2), and bicyclo[4.2.1]-l(2)-nonene (3) by the intramolecular Wittig reaction is described (see Schemes 1-4). The (3-oxocycloalkyl)alkyl-phosphonium bromides 20, 27 and 38 undergoing cyclization to the bridgehead olefins are formed by simple reaction sequences. The spectral properties (IR., lH-NMR., W-NMR., and UV.) of the olefins are discussed with regard to their strain.Introduction. -Considerable interest has been shown recently in defining the limits of Bredt's rule and in predicting the degree of strain in bridgehead double bonds [2] [3]. Bredt himself had limited his qualitative statement, that a double bond at the bridgehead is not possible, to bicyclic olefins of the pinane and camphane series and related compounds [4]. Later Prelog demonstrated that larger bicyclic ring systems indeed can accommodate a bridgehead double bond [5]. Based on this research, Fawcett drew the conclusion that compounds with a double bond at the bridgehead cannot be isolated if the total number of bridge atoms S2) is less than nine [6].In 1967, both Wiseman [7] and Marshall [8] reported the successful synthesis of bicyclo[3.3. I]-l(2)-nonene (l), a reactive but stable bridgehead olefin with seven bridge carbon atoms only. Wiseman emphasized that the stability of a bridgehead olefin is related to the stability of the largest trans-cycloalkene from which it can be derived formally by bridging. Since trans-cyclooctene is a stable, isolable compound [I 11, and the increasing number of synthetic approaches to even more strained bridgehead olefins [3].

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Section: Experimental Partmentioning

confidence: 56%

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confidence: 99%

ChemInform Abstract: THE SYNTHESIS OF STRAINED METHYLENE‐BRIDGED BICYCLIC OLEFINS BY THE INTRAMOLECULAR WITTIG REACTION

Becker¹

1977

Chemischer Informationsdienst

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“…The preferential formation of the presumably less stable compound ( 4 ) [ ( 4 ) and ( 5 ) are formed in the ratio of 5: 1 respectively] during the thermolysis (3) is attributable to the stereoelectronically favored syn-elimination in the fivemembered ring. The third possible olefin would be a derivative of trans-cyclohexene and as such would possess considerable strain energy.…”

Section: Eliminationsmentioning

confidence: 99%

Methods for the Preparation of Bridgehead Olefins

Keese

1975

Angew. Chem. Int. Ed. Engl.

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During the past eight years, bridgehead olefins have attracted rapidly increasing attention. In view of their significance with regard to the stereochemistry of aikenes, the study of certain reaction mechanisms, and the nature of the double bond, detailed research into this structural type appears highly desirable. Bridgehead olefins represent connective linkages between olefins in the ground state and species which can arise in the deactivation of photochemically excited alkenes and cycloalkenes and also contribute to our understanding of the structural conditions prevailing during cis-trans isomerization of alkenes.

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“…-The strain inherent in the double bond of bridgehead olefins such as the bicyclononenes 1, 2 and 3 [I] should lead to an enhanced reactivity in addition reactions compared to other, unstrained trisubstituted olefins. Indeed, as shown by Wiseman [2] and Marshall [3], bicyclo[3.3.l]-1(2)-nonene (1) reacts extremely fast with electrophilic reagents, e.g. acetic acid, water or alcohol in the presence of an acid catalyst, bromine, osmium tetroxide, peracid, and diborane.…”

mentioning

confidence: 99%

“…0.998, the standard deviation f 5%. (3) could be analysed without prior neutralization of the acid. 13.5 p1 of a mixture of olefin 2 or 3 (0.050 mmol) and tridecane were injected into 0.50 ml of acetic acid under nitrogen.…”

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confidence: 99%

Electrophilic Additions to Strained Bridgehead Olefins. Estimation of Strain by Comparison with the Solvolysis of Bridgehead Bromides

Becker¹

1977

Helvetica Chimica Acta

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SummaryThe addition of water, acetic acid, and hydrogen bromide to the strained bridgehead olefins bicyclo[3.3.1]-1(2)-nonene (l), bicyclo[4.2. I]-l(8)-nonene (2), and bicyclo[4.2.1]-1(2)-nonene (3) gives exclusively the bridgehead alcohols, acetates, and bromides, respectively. The reaction rate constants for the addition of acetic acid to the bridgehead olefins 1, 2 and 3, and the solvolysis rates for the related I-bromobicyclo[3.3.l]nonane (4) and 1-bromobicyclo[4.2. llnonane (5) were measured. A comparison of the activation enthalpies of these two reactions gives an estimate of relative strain of the bridgehead double bond. The strain in the bicyclo[4.2. llnonenes 2 and 3 is similar to that in trans-cyclooctene (8-9 kcal/mol).Introduction. -The strain inherent in the double bond of bridgehead olefins such as the bicyclononenes 1, 2 and 3 [I] should lead to an enhanced reactivity in addition reactions compared to other, unstrained trisubstituted olefins. Indeed, as shown by Wiseman [2] and Marshall [3], bicyclo[3.3.l]-1(2)-nonene (1) reacts extremely fast with electrophilic reagents, e.g. acetic acid, water or alcohol in the presence of an acid catalyst, bromine, osmium tetroxide, peracid, and diborane. A reaction was also observed with the nucleophilic reagents methyllithium and phenyllithium, with the dipolarophile diazomethane, and with some dienes yielding Diels-Alder adducts.

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Bicyclo[3.3.1]non-1-ene

Cited by 46 publications

References 1 publication

ChemInform Abstract: THE SYNTHESIS OF STRAINED METHYLENE‐BRIDGED BICYCLIC OLEFINS BY THE INTRAMOLECULAR WITTIG REACTION

ChemInform Abstract: THE SYNTHESIS OF STRAINED METHYLENE‐BRIDGED BICYCLIC OLEFINS BY THE INTRAMOLECULAR WITTIG REACTION

Methods for the Preparation of Bridgehead Olefins

Electrophilic Additions to Strained Bridgehead Olefins. Estimation of Strain by Comparison with the Solvolysis of Bridgehead Bromides

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