Tandem 1,3-dipolar cycloaddition of mesoionic 2,4-diphenyl-1,3-oxathiolium-5-olate with cycloocta-1,5-diene. A new synthesis of the tetracyclo[6.2.0.04,10.05,9]decane ring system

Sponholtz, William R.; Trujillo, Hernando A.; Gribble, Gordon W.

doi:10.1016/s0040-4039(00)00042-3

Cited by 8 publications

(3 citation statements)

References 34 publications

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“…184 Caged hydrocarbon 218 (Scheme 73) has been synthesized in an almost quantitative yield via photoextrusion of SO 2 in sulfone 217 upon irradiation in an acetone-benzene 1:1 mixture. 185 Photogenerated biradicals were the key intermediates in the preparation of the Stemona alkaloid (±)-neostenine (222,Scheme 74). The irradiation caused the cleavage of the C−N bond in maleimide 219 and the fused pyrrolo[1,2-a]azepine core in 221 was formed by an intramolecular [5 + 2] photocycloaddition.…”

Section: Two or Three Ringsmentioning

confidence: 99%

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Carbon–Carbon Bond Forming Reactions via Photogenerated Intermediates

2016

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The present review offers an overview of the current approaches for the photochemical and photocatalytic generation of reactive intermediates and their application in the formation of carbon-carbon bonds. Valuable synthetic targets are accessible, including arylation processes, formation of both carbo- and heterocycles, alpha- and beta-functionalization of carbonyls, and addition reactions onto double and triple bonds. According to the recent advancements in the field of visible/solar light catalysis, a significant part of the literature reported herein involves radical ions and radicals as key intermediates, with particular attention to the most recent examples. Synthetic application of carbenes, biradicals/radical pairs and carbocations have been also reported.

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Section: Two or Three Ringsmentioning

confidence: 99%

“…Caged hydrocarbon 218 (Scheme ) has been synthesized in an almost quantitative yield via photoextrusion of SO 2 in sulfone 217 upon irradiation in an acetone-benzene 1:1 mixture …”

Section: Formation Of a Ringmentioning

confidence: 99%

Carbon–Carbon Bond Forming Reactions via Photogenerated Intermediates

2016

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“…The most common process after a-cleavage is bond formation at the oxygen atom to form the corresponding sulfenates, RS-OR 0 . [54] and 88 [55] give the photoelimination and CÀC bond-formation products 87 and 89, respectively, in yields that vary from 88% to 95%. In contrast, when the sulfone moiety is part of a lactam (90), the formation of b-lactam 91 occurs in only 10% yield.…”

Section: Photoelimination Of Co 2 From Lactonesmentioning

confidence: 99%

CarbonCarbon Bond Formation by the Photoelimination of Small Molecules in Solution and in Crystals

Shiraki

2009

Handbook of Synthetic Photochemistry

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The formation of CÀC bonds is arguably the most important reaction in organic synthesis. While many strategies have been developed to link organic fragments with a wide range of thermal processes, photochemical syntheses based on the elimination of a small molecule, X (Scheme 2.1), offer significant advantages when the desired structures are highly strained or hindered. In this chapter, we will describe examples of the generation of CÀC bonds through the photoinduced extrusion of small molecules such as N 2 , CO 2 , CO, and SO 2 , as well as the formal extrusion of S atoms. After describing the most general mechanistic aspects covering these reactions and the current scope and limitations, we will illustrate examples involving these reactions in solution. Following that, we will describe a strategy based on the use of crystalline solids that helps to control the fate of the reaction intermediates. Finally, we will illustrate the use of crystalline ketones (X¼CO) as one of the most promising general methods for the synthesis of compounds with all-carbon adjacent stereogenic quaternary centers.The photoelimination of a small stable molecule X accompanied by the formation of a new CÀC bond could, in principle, take place in a concerted manner through cyclic transition states with simultaneous bond-breaking and bond-making steps that follow trajectories determined by orbital symmetry considerations. However, as it pertains to photodecarbonylation reactions, theoretical analysis on the formation of hydrogen and CO from formaldehyde suggests that the concerted process is significantly less likely than the stepwise cleavage of the HÀC(O)ÀH bonds [1]. Similar conclusions have been made for the elimination of N 2 and H 2 from simple diazene (HN¼NH) [2]. In fact, evidence for concerted reactions is available only in a handful of cases (vide infra). Most examples involve a four-step process that starts with electronic excitation (step 1) and is followed by an a-cleavage reaction (step 2) to give a primary biradical or radical pair (BR-1). Subsequent dissociation of the small molecule X (step 3) results in the formation of the secondary biradical or radical pair (BR-2), which is followed by radical-radical combination to give the desired product (step 4).Handbook of Synthetic Photochemistry. Edited

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Photogeneration of Biradicals and Radical Pairs

2013

Photochemically‐Generated Intermediates in Synthesis

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Tandem 1,3-dipolar cycloaddition of mesoionic 2,4-diphenyl-1,3-oxathiolium-5-olate with cycloocta-1,5-diene. A new synthesis of the tetracyclo[6.2.0.04,10.05,9]decane ring system

Cited by 8 publications

References 34 publications

Carbon–Carbon Bond Forming Reactions via Photogenerated Intermediates

Carbon–Carbon Bond Forming Reactions via Photogenerated Intermediates

CarbonCarbon Bond Formation by the Photoelimination of Small Molecules in Solution and in Crystals

Photogeneration of Biradicals and Radical Pairs

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