A general method for iterative cyclopentannulation: sequential use of Claisen rearrangement and radical enyne closure

Clive, Derrick L. J.; Manning, Hartford W.

doi:10.1039/c39930000666

Cited by 9 publications

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References 33 publications

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“…In the preliminary communication (ref b) footnote a of Scheme 2 should refer to the anti isomer, and footnote b should refer to the syn isomer. Stereochemical assignments to the epoxides were made by NOE measurements on the derived ketone 85 β (see the Experimental Section for 85 β).…”

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confidence: 99%

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Cyclopentannulation by an Iterative Process of Sequential Claisen Rearrangement and Enyne Radical Closure: Routes to Triquinane and Propellane Systems and Use in the Synthesis of (±)-Ceratopicanol

et al. 1996

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Cycloalkenyl acetylenes 4, which are easily prepared from allylic alcohols by Claisen rearrangement and homologation (1 → 4), generally undergo radical cyclization (4 → 6) on treatment with stannyl radicals. The products (6) can themselves be converted into allylic alcohols, so that the annulation sequence can then be repeated. In certain cases enyne cyclization initiated by stannyl radicals does not work, but an alternative process (cf. Scheme 9) of epoxide opening with bis(cyclopentadienyl)titanium(III) chloride can then be used. Di- and triquinanes (Scheme 3) were made by the stannyl radical approach; the epoxide route was used to prepare a simple propellane (Scheme ) and in a synthesis of (±)-ceratopicanol (Schemes and 9).

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Section: Referencesmentioning

confidence: 99%

“…We report a procedure for fusing a five-membered ring onto a cyclic allylic alcohol . The method, which is an iterative one, has been used to construct members of the triquinane class; a slight modification gave a propellane, and the modified procedure was used to synthesize the sesquiterpene (±)-ceratopicanol.…”

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Cyclopentannulation by an Iterative Process of Sequential Claisen Rearrangement and Enyne Radical Closure: Routes to Triquinane and Propellane Systems and Use in the Synthesis of (±)-Ceratopicanol

et al. 1996

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ChemInform Abstract: A General Method for Iterative Cyclopentannulation: Sequential Use of Claisen Rearrangement and Radical Enyne Closure.

Clive

Manning

1993

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A General Method for Iterative Cyclopentannulation: Sequential Use of Claisen Rearrangement and Radical Enyne Closure. -A general method for the construction of anellated cyclopentanes such as (VI) involves Claisen rearrangement of the allyl ether derived from the alcohol (I) and the conversion of the thereby formed aldehyde (III) into the terminal acetylene (V) followed by cyclization. The procedure is iterative, since (VI) can be converted into the alcohol ( VIII) which, in turn, undergoes a similar sequence to give the twofold anellated product (X). -(CLIVE, D. L. J.; MANNING, H. W.; J.

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Transition Metal‐Assisted Transformations of Diversely Functionalized Dienynes

et al. 2003

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We report the triphenyltin-mediated free-radical cyclization of 4-ethynyl-2,6,6-trimethylocta-1,7-dien-4-ol (1) and 4-ethynyl-6,6-dimethylocta-1,7-dien-4-ol (2), along with some chemical manipulations of the resulting stannylidene derivatives 3 and 7. The reaction of intermediates 3 and 7 with BuLi afforded the protodestannylated compounds 5 and 8, respectively, in good yield, while the reaction of the mixture of adducts 3 and 4 with iodine gave the chloro(diphenyl)stan-

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A general method for iterative cyclopentannulation: sequential use of Claisen rearrangement and radical enyne closure

Abstract: Cycloalkenyl acetylenes 4, which are easily prepared from allylic alcohols 1, undergo radical cyclization (4 -+ 5) on treatment with stannyl radicals; the products 5 are themselves convertible into allylic alcohols, so that the annulation sequence can be repeated.

Cited by 9 publications

References 33 publications

Cyclopentannulation by an Iterative Process of Sequential Claisen Rearrangement and Enyne Radical Closure: Routes to Triquinane and Propellane Systems and Use in the Synthesis of (±)-Ceratopicanol

Cyclopentannulation by an Iterative Process of Sequential Claisen Rearrangement and Enyne Radical Closure: Routes to Triquinane and Propellane Systems and Use in the Synthesis of (±)-Ceratopicanol

ChemInform Abstract: A General Method for Iterative Cyclopentannulation: Sequential Use of Claisen Rearrangement and Radical Enyne Closure.

Transition Metal‐Assisted Transformations of Diversely Functionalized Dienynes

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