Mechanism of adamantane rearrangements

Engler, Ekkehard; Farcasiu, M.; Sevin, A.; Cense, J. M.; Schleyer, Paul V. R.

doi:10.1021/ja00798a059

Cited by 95 publications

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“…Whitlock et al [15] proposed a network of conceivable pathways which consists of 1.2-shifts only. One of these pathways was given preference by Schleyer on the basis of molecular mechanics calculations [16]. The Table I (continued).…”

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confidence: 99%

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The Principle of Minimum Chemical Distance and the Principle of Minimum Structure Change

Jochum

Gasteiger

Ugi

1982

Zeitschrift Für Naturforschung B

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AbstractThe principle of minimum chemical distance (PMCD) is derived from the general theory of the BE- and R-matrices, and makes precise the vague classical “principle of minimum structure change”. In fact, the PMCD may be seen as the principle of minimum structure change in mathematical terms. It provides a quantitative measure of chemical similarity of isomeric molecular systems. Its applications lie in the fields of correlations of substructures, elucidation of reaction mechanisms, and evaluation of synthetic pathways as is illustrated by examples. The mathematical foundations of the computer assisted application of the PMCD are presented.

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“…Thus if the reaction proceeded from hydrocarbon to hydrocarbon, the bonds indicated in bold face in 1 would be broken and the one in 2 would be 26 made. In comparison the sum of the CD of the individual steps of the shortest pathway which has been previously considered by Schleyer [16] is 20.…”

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The Principle of Minimum Chemical Distance and the Principle of Minimum Structure Change

Jochum

Gasteiger

Ugi

1982

Zeitschrift Für Naturforschung B

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“…was distilled off through a Vigreux column. From the residue, 71 mg (70%) of 3 [2] [7] were isolated by prep. GLC (B: 120").…”

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confidence: 99%

The adamantane rearrangement of 1,2‐trimethylenenorbornanes. Part V. Rearrangements of 1,2‐trimethylenenorbornanes initiated by regioselective formation of carbocation centers at C(2) and C(6)

Klester¹,

Ganter²

1985

Helvetica Chimica Acta

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The behaviour of the regioselectively generated carbocation centers at C(2) and C(6) in 1,2-trimethylenenorbornanes was investigated in order to study the occurrence or absence o f a degenerate rearrangement EF?M in the adamantane rearrangement of both 1,Zendo-(1) and 1,2-exo-trimethylenenorbornane (2) to 2-endo,6-endo-trimethylenenorbornane (3). A degenerate rearrangement E e M is inevitably involved inasmuch as a 1,2-trimethylenenorborn-2-yl cation E not only is formed directly as manifested by the conversions of the reactants 4 (C(2), C(3)-olefin) and 6 (C(2), C(3')-olefin), but also indirectly (via F-E) if the leaving group at C(6) to be ionized occupies the endo-position (dendo-alcohol 8). No degenerate rearrangement E@M is operative starting from reactants that lead directly to a 2,6-trimethylenenorborn-2-y1 cation G ; this is the case with both the ionization of the 6-exo-alcohol 10 having the leaving OH-group in a stereoelectronically favoured configuration to undergo simultaneous C(I),C(2)-bond migration (-G) as well as the protonation of the olefin 13 which is followed by the same reaction pathway.1. Introduction. -In the adamantane rearrangement of both 1,a-endo-(l),) and 1,Zexo -trimethylenenorbornane (2)2) to 2-endo,6-endo-trimethylenenorbornane (3)*), a degenerate rearrangement (EsM3); Scheme 2) is involved as verified from treatment of D-labelled 1 ,2-endo -, 1,2-exo-, and 2-endo,6-endo -trimethylenenorbornane (D-labelled 1,

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“…, who described 1 as an 'energetic bottle neck [4]', studied the AlBr,-catalyzed isoinerization of 1 (calc. AH: = -10.88 kcal/mol [5]) and observed that it behaves as a 'continental divide', rearraging both 'backwards' to 2-exo,3-exo -trimethylene-8,9,1O-tri- Srkeme …”

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The Adamantane Rearrangement of Tricyclo[4.2.2.0^1,5]decane to Tricyclo[5.3.0.0^4,8]decane

Ghatak¹,

Ganter²

1988

Helvetica Chimica Acta

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Mechanism of adamantane rearrangements

Cited by 95 publications

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The Principle of Minimum Chemical Distance and the Principle of Minimum Structure Change

The Principle of Minimum Chemical Distance and the Principle of Minimum Structure Change

The adamantane rearrangement of 1,2‐trimethylenenorbornanes. Part V. Rearrangements of 1,2‐trimethylenenorbornanes initiated by regioselective formation of carbocation centers at C(2) and C(6)

The Adamantane Rearrangement of Tricyclo[4.2.2.0^1,5]decane to Tricyclo[5.3.0.0^4,8]decane

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Mechanism of adamantane rearrangements

Cited by 95 publications

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The Principle of Minimum Chemical Distance and the Principle of Minimum Structure Change

The Principle of Minimum Chemical Distance and the Principle of Minimum Structure Change

The adamantane rearrangement of 1,2‐trimethylenenorbornanes. Part V. Rearrangements of 1,2‐trimethylenenorbornanes initiated by regioselective formation of carbocation centers at C(2) and C(6)

The Adamantane Rearrangement of Tricyclo[4.2.2.01,5]decane to Tricyclo[5.3.0.04,8]decane

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The Adamantane Rearrangement of Tricyclo[4.2.2.0^1,5]decane to Tricyclo[5.3.0.0^4,8]decane