Carbonium ion rearrangements in the deltacyclane ring system

Freeman, Peter K.; Balls, Dean M.; Blazevich, Joseph N.

doi:10.1021/ja00710a043

Cited by 19 publications

(5 citation statements)

References 10 publications

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“…Furthermore, the tetracyclic parent system in 25, commonly known as "deltacyclane," has no particular strain disfavorability and considerable investigation of the system has been reported. 30 If ion 25 is involved, the cyclopropyl ring opening must be subsequent to the aryl participation. Contrariwise, two experimental facts argue that the cyclopropyl ring opening must be simultaneous with the aryl participation.…”

Section: Discussionmentioning

confidence: 99%

Electrocyclic effects in solvolysis. I. Aryl participation and cyclopropyl ring opening in the solvolysis of exo-3,3-diaryltricyclo[3.2.1. 0.2,4]oct-8-yl tosylates

Wilt¹,

Malloy²,

Mookerjee³

et al. 1974

J. Org. Chem.

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To seek a unique combination of anchimeric participation and electrocyclic ring opening in solvolysis reactions, a number of tosylates of the title were prepared and characterized. The anti-8 tosylates indeed do undergo hydrolysis and acetolysis with concomitant 1,4-aryl migration by the Ari-5 route and cyclopropyl ring opening to afford novel 3,syn-8-diarylbicyclo[3.2.1]oct-3-en-2-ols. The structures of these products were established by various means, among them ozonation to ci's-2-arylcyclopentane-cis-l,3-dicarboxylic acids (cí's-2-arylnorcamphoric acids). Although ~7000-fold as fast in solvolysis as their nonphenyl analogs (evidence for anchimeric participation), the anti-8 tosylates exhibit a low p value (-1.68 for hydrolysis and -1.3 for acetolysis) among themselves. This fact, together with the slight rate retardation caused by the introduction of a C-6,7 double bond, indicates considerable concertedness in the aryl migration and cyclopropyl ring opening processes. An example of a syn-8 tosylate of the title was found to rearrange differently, following a combination of paths most closely related to that reported for syn-7-norbornenyl tosylate. Because this path does not involve aryl participation in the slow step, this syn-8 tosylate was essentially equal in rate to its nonphenyl analog.

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Section: Discussionmentioning

confidence: 99%

Electrocyclic effects in solvolysis. I. Aryl participation and cyclopropyl ring opening in the solvolysis of exo-3,3-diaryltricyclo[3.2.1. 0.2,4]oct-8-yl tosylates

Wilt¹,

Malloy²,

Mookerjee³

et al. 1974

J. Org. Chem.

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“…A variety of derivatives (brosylates, chlorides, amines) of both stereoisomers gave 125-OAc as the sole product of acetolysis or of deamination in acetic acid.103,104 Solvolysis of the exo isomer is characterized by a rate enhancement (Table VII), complete scrambling of a deuterium label initially on C-8 (or C-9) between C-8 and C-4 (or C-9 and C-5),104 a relatively low secondary deuterium isotope effect for an exo deuterium atom on C-9,105 and complete retention of optical activity in the product formed from acetolysis of an active sample of 125-OBs. 104 These results, and the nmr spectrum of the cation formed by dissolving either 125-OH or 126…”

Section: Starting Brosylatementioning

confidence: 77%

Long-Range Interactions of Cyclopropyl Groups with Carbonium Ion Centers

Haywood-Farmer¹

1974

Chem. Rev.

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“…Cie«i5«D2 °As neat film. 6 For hydrogen numbering, see Scheme I; bs = broad s, bt = broad t, cm = complex m. c Satisfactory analytical data for C, , N (±0.3%) were provided for these compounds. Ed.…”

Section: Resultsmentioning

confidence: 99%