Diastereoselective synthesis of 1,2-O-isopropylidene-1,6-dioxaspiro[4,4]nonane applying the methodology of generation of radical cations under non-oxidizing conditions

Sartillo‐Piscil, Fernando; Vargas, Mónica Andrea; Parrodi, Cecilia Anaya de; Quintero, Leticia

doi:10.1016/s0040-4039(03)00817-7

Cited by 26 publications

(7 citation statements)

References 14 publications

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“…Both of these processes take place with a high degree of retention of configuration at phosphorus, indicative of the short lifetimes of the contact radical ion pair. The incorporation of suitable nucleophiles, particularly allylamines, in the system enables trapping of the alkene radical cation in tandem polar/radical crossover reactions leading to the formation of numerous alkaloid skeletons and other heterocyclic systems . If nucleophilic trapping of the alkene radical cation is to compete effectively with formation of the rearranged radical in nonpolar solvents, then it must necessarily take place at the level of the initial contact radical ion pair.…”

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confidence: 99%

Enantioselective Cyclization of Alkene Radical Cations

2003

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[reaction: see text] Enantiomerically enriched beta-(diphenylphosphatoxy)nitroalkanes undergo radical ionic fragmentation, induced by tributyltin hydride and AIBN in benzene at reflux, to give alkene radical cations in contact radical ion pairs. These contact ion pairs are trapped intramolecularly by amines to give pyrrolidines and piperidines with significant enantioselectivity ( approximately 60% ee), indicative of cyclization competing effectively with equilibration within the ion pairs. Use of an intramolecular N-propargylamine as a nucleophile provides an enantiomerically enriched pyrrolizidine skeleton via a tandem polar/radical crossover sequence.

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confidence: 99%

Enantioselective Cyclization of Alkene Radical Cations

2003

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“…Selective deprotection of the primary acetonide of diacetone glucose 29 followed by diol cleavage with periodic acid afforded aldehyde 33 . The intermolecular Wittig reaction of aldehyde 33 with ylide 34 resulted in the isolation of the ( Z )-ester as the unsaturated lactone 32 in 39% yield as well as ( E )-ester 35 in 23% yield . The former was reduced to 23 as shown above.…”

Section: Resultsmentioning

confidence: 82%

Total Synthesis of Herbicidin C and Aureonuclemycin: Impasses and New Avenues

et al. 2013

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The undecose nucleoside antibiotics herbicidin C and aureonuclemycin are biologically highly active and represent challenging targets for total synthesis. Herein, the gradual evolution of our synthetic strategy toward these natural products is described in detail. The initial route encompasses metalate addition chemistry but suffers from poor stereochemical control. In contrast, the ultimately successful strategy benefits from a variety of reagent-controlled stereoselective transformations, including a surprisingly facile and highly diastereoselective N-glycosylation process. The presented work also describes new building blocks that might find further application in carbohydrate chemistry.

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“…The THF building blocks 1 – 4 were synthesized by using our previous reported method 40a. The chlorovinyl compounds were obtained from THF derivatives 1 – 4 by their sequential hydrolysis–oxidation Wittig olefination (SHOWO) 41,45. Hydrolysis–oxidation of domains by 1.2 equiv.…”

Section: Resultsmentioning

confidence: 99%

Studies on Tetrahydrofuran‐Based Highly O‐Functionalized Alkynes: Applications to Synthesis of Tetrahydrofuranyl‐Polyynes and C‐Nucleoside Analogues

et al. 2011

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The enantiomerically pure tetrahydrofuranylalkynes 17-20 were synthesized by using various methods. By utilizing these alkynes, an efficient CuI-catalysed sp-sp carbon homocoupling protocol in dry DMF without other additives (like amine or base, phosphane and palladium catalyst) has been developed. The method has been applied to the synthesis of symmetrical butadiynyl (32-37), octatetraynyl (47) and dodecahexaynyl (49) polyynes. The unsymmetrically substi-

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Diastereoselective synthesis of 1,2-O-isopropylidene-1,6-dioxaspiro[4,4]nonane applying the methodology of generation of radical cations under non-oxidizing conditions

Cited by 26 publications

References 14 publications

Enantioselective Cyclization of Alkene Radical Cations

Enantioselective Cyclization of Alkene Radical Cations

Total Synthesis of Herbicidin C and Aureonuclemycin: Impasses and New Avenues

Studies on Tetrahydrofuran‐Based Highly O‐Functionalized Alkynes: Applications to Synthesis of Tetrahydrofuranyl‐Polyynes and C‐Nucleoside Analogues

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