Synthesis and characterization of some polycyclic cyclobutanones

Miller, Robert D.; DOLCE, D. L.; MERRITT, V. Y.

doi:10.1021/jo00869a030

Cited by 32 publications

(10 citation statements)

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“…During the preparation of the racemic tricyclic acyloin 3-hydroxytricyclo[4.2.1.0 2,5 ]non-7-en-4-one (±)-3 starting from endo-2,3-bis(methoxycarbonyl)bicyclo[2.2.1]hept-5-ene 1 by employing the acyloin condensation, 1 we observed 2 that an acid hydrolysis of the bis-trimethylsilyloxy intermediate 2 furnished stereoselectively the single racemic acyloin (±)-3 having an endo-hydroxy group (Scheme 1). † The endo-hydroxy configuration of 3 did not change even in the presence of triethylamine, which brought about complete deuterium exchange of the methine hydrogen on the acyloin functionality with deuterium oxide within 10 h. This seemed to be due to facile equilibration between the acyloin 3 and the transient meso-1,2-enediol intermediate 4 followed by convex-face selective protonation of the latter under weak basic conditions.…”

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confidence: 99%

Lipase–triethylamine-mediated dynamic transesterification of a tricyclic acyloin having a latent meso-structure: a new route to optically pure oxodicyclopentadiene

Taniguchi¹,

Ogasawara²

1997

Chem. Commun.

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Lipase–triethylamine-mediated dynamic transesterification of a tricyclic acyloin having a latent meso-structure: a new route to optically pure oxodicyclopentadiene

Taniguchi¹,

Ogasawara²

1997

Chem. Commun.

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“…All structural assignments rest firmly on analytical and spectral data. Dimide reductions of the ethers 7 and 14 produced the saturated derivatives 11 and 16, respectively, whose spectral data were compared with those of Kirmse and co-workers.13 In every case, the homoallylic and cyclopropylcarbinyl derivatives were separated by careful column chromatography on AgN03-silica gel (see Experimental Section) prior to characterization.…”

Section: Discussionmentioning

confidence: 99%

“…The desired cyclobutanones were all prepared as previously described. 7 The inside cyclobutanol derivatives were prepared from the corresponding cyclobutanone derivatives by treatment with sodium borohydride in ethanol. The crude carbinol product was recovered in the usual manner and was generally pure enough for subsequent transformations.…”

Section: Experimental Section26mentioning

confidence: 99%

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Solvolyses of polycyclic cyclobutyl toluenesulfonate derivatives

Diaz¹,

Miller²

1978

J. Am. Chem. Soc.

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A number of isomeric 3-tosyloxytricylo[4.2.1,02•5] non-7-enes and their corresponding saturated analogues have been prepared and solvolyzed. The chemical behavior of these ROTs esters is of particular interest because the influence of the remote double bond on the developing cation can be tested. In the case of the inside esters (i.e., inside, endoand exo-1-OTs), the highly strained 2,5 bond opens in a disrotatory fashion to generate cyclopropylcarbinyl-type rearrangement products. Consistently, the stereochemistry of the actual cyclopropylcarbinyl products mirrors that of the starting material. In the case of the unsaturated esters inside, endoand exo-1-OTs, the presence of the remote double bonds results in only an inductive rate retardation relative to the corresponding saturated derivatives. The epimeric outside, endoand exo-1-OTs and the corresponding saturated derivatives solvolyze very slowly with little evidence of 2,5-bond opening. The outside, endo-l-Ols, is the only case where the remote double bond produces relative rate enhancement. The extensive skeletal reorganization in the solvolysis of the rearranged tosylate 6 again illustrates the importance of orbital alignment in the ground state for participation in the course of a solvolysis reaction.

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“…In an NMR study of IX ^X, Miller concluded that the major reason for the thermodynamic stability of enols IX (when R = i-Pr, IX can be isolated as orange needles, m.p. 182-186°C) was steric destabilization of the keto form X as a consequence of interaction between the ortho R groups and the 7r-cloud of the naphthalene ring (10).…”

Section: Mes-c-c-mesmentioning

confidence: 99%