Formation of trans ring-fused compounds by an alkylation-radical cyclization sequence

Clive, Derrick L. J.; Manning, Hartford W.; Boivin, Taryn L. B.; Postema, Maarten H. D.

doi:10.1021/jo00076a057

Cited by 39 publications

(6 citation statements)

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“…This methodology has also been applied to more complex molecules. − One particular step of the total synthesis of the diterpenoid atractyligenin, which was reported by Corey and co-workers, is noteworthy in this context. Scheme shows that slow addition of the reducing agent over 12 h to a solution of selenocarbonate 314 gives the γ-lactone 315 in a 73% yield.…”

Section: A Alkoxycarbonyl Radicalsmentioning

confidence: 99%

Chemistry of Acyl Radicals

et al. 1999

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Section: A Alkoxycarbonyl Radicalsmentioning

confidence: 99%

Chemistry of Acyl Radicals

et al. 1999

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“…However, only axial radical 45 can undergo cyclization through an electronically favored anti transition structure [15] to give the major product observed. [16] Axial radical 47 may undergo radical interconversion [13b] to give an equatorial radical that then cy- clizes in a less selective fashion. Ring interconversion between 47 and 45 may also occur but this would be expected to have a higher energy barrier than radical interconversion.…”

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confidence: 99%

Selective Reductions of Cyclic 1,3‐Diesters by Using SmI₂ and H₂O

Collins

Oliveira

Guazzelli

et al. 2010

Chemistry A European J

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SmI(2)/H(2)O reduces cyclic 1,3-diesters to 3-hydroxyacids with no over reduction. Furthermore, the reagent system is selective for cyclic 1,3-diesters over acyclic 1,3-diesters, and esters. Radicals formed by one-electron reduction of the ester carbonyl group have been exploited in intramolecular additions to alkenes. The ketal unit and the reaction temperature have a marked impact on the diastereoselectivity of the cyclizations. Cyclization cascades are possible when two alkenes are present in the starting cyclic diester and lead to the formation of two rings and four stereocenters with excellent stereocontrol.

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“…[2] These are not directly accessible by the Diels-Alder reaction, which usually is the most important "working horse" in their synthesis. [3] We now report on a novel approach which is based on the asymmetric homoaldol reaction, [4] coupled with diastereoselective g-lactone enolate alkylation [5] and ring-closing olefin metathesis. [6] Moreover, at both bridgehead positions, stereogenic quaternary carbon centres are created.…”

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confidence: 99%