On the Paternò–Büchi reaction of chiral phenylglyoxylate esters with furan derivatives

D’Auria, Maurizio; Emanuele, Lucia; Racioppi, Rocco

doi:10.1039/b302883f

Cited by 34 publications

(31 citation statements)

References 25 publications

(23 reference statements)

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“…Furthermore, we have to note that the reaction showed a high regio-and stereochemical control. The high stereoselectivity here observed in particular in the case of the dimerization of compound (24) was not described before.…”

Section: Methodsmentioning

confidence: 52%

The photochemical dimerization of 3-heteroaryl-acrylates

D’Auria¹,

Emanuele²,

Esposito³

et al. 2002

Arkivoc

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A detailed explanation of the observed photochemical reactivity of 3-heteroaryl-acrylates is furnished on the basis of a comprehensive review of the photochemical dimerizations of this type of compounds. The reactions occurred in the triplet state of the reagents showing good regio-and stereoselectivities. The regioselectivity can be explained assuming that the dimerization reaction is frontier orbitals controlled. The reaction of the triplet state of a reagent with another molecule of the reagent leads to the formation of the most stable biradical. This behavior induces a control in the relative stereochemistry of the two ester functions. The following cyclization occurs in order to obtain the products under kinetic control. This cyclization allows the formation of the most stable isomers.

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Section: Methodsmentioning

confidence: 52%

The photochemical dimerization of 3-heteroaryl-acrylates

D’Auria¹,

Emanuele²,

Esposito³

et al. 2002

Arkivoc

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“…As expected, esterification of commericially available uracanic acid (16, Scheme 1) followed by benzophenone-sensitized photodimerization 22 proceeded in good yield to give all-trans cyclobutane 15. Interestingly, attempts at photodimerization of the methyl ester analogue of 14 under similar conditions gave a mixture of stereoisomers.…”

Section: First Generation Approach To Sceptrinmentioning

confidence: 80%

Total Synthesis of Dimeric Pyrrole−Imidazole Alkaloids: Sceptrin, Ageliferin, Nagelamide E, Oxysceptrin, Nakamuric Acid, and the Axinellamine Carbon Skeleton

et al. 2007

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The dimeric pyrrole imidazole natural products are a growing class of alkaloids with exotic connectivity, unique topologies, high nitrogen content, and exciting bioactivities. This full account traces the evolution of a strategy that culminated in the first total syntheses of several members of this family, including sceptrin, ageliferin, nagelamide E, nakamuric acid (and its methyl ester), and oxysceptrin. Details on the fascinating conversion of sceptrin to ageliferin, which has been used to produce gram quantities of this sensitive natural product, are provided. In addition, the first enantioselective total synthesis of sceptrin and ageliferin are reported by programming the fragmentation of an oxaquadricyclane. A hallmark of our approach to this family of alkaloids is the minimal use of protecting groups despite the presence of 10 nitrogen atoms in the target compounds. Thus, the fundamental chemistry of the 2-aminoimidazole heterocycle was explored without masking its innate reactivity. Insights gained during these explorations led to total syntheses of oxysceptrin and nakamuric acid and a successful construction of the carbon skeleton of axinellamine.

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“…Introducing chiral auxiliary in the molecule making more simple the attack on a prochiral face of the substrate; examples have been reported on 2+2 cycloadditons (Scheme 12) [42][43][44][45][46][47][48][49][50], and in photocyclization (Norrish Type II reaction) [51,52]. 2.…”

Section: Molecules With Prevented Mobilitymentioning

confidence: 98%

Concepts of Stereoselective Photochemistry and a Case Study: the Paterno-Buchi Reaction

D’Auria¹,

Racioppi

2009

COC

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The main methods reported in literature to obtain stereoselective photochemical reaction is reviewed. The most important approached attempted to obtain stereoselective photochemical reaction are:1.) the use of diastereoselective photochemical reactions, 2.) the use of molecules with prevented mobility (this approach can be obtained 1. introducing chiral auxiliary, 2. introducing chiral molecules in the reaction mixture able to give complexes with a reduced mobility, 3. performing the reaction in organized media such as zeolites or cyclodextrins, 4. performing the reaction on single crystal, 5. performing the reaction on single crystals of molecules able to give crystal in chiral space group, and, 6. finally performing the reaction in solid phase on inclusion complexes of the substrate with chiral molecules); 3.) using chiral solvents and chiral light, and 4.) using chiral photosensitizers.The case of the diastereoselective Paternò-Büchi reaction on furan derivatives is also discussed.

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On the Paternò–Büchi reaction of chiral phenylglyoxylate esters with furan derivatives

Cited by 34 publications

References 25 publications

The photochemical dimerization of 3-heteroaryl-acrylates

The photochemical dimerization of 3-heteroaryl-acrylates

Total Synthesis of Dimeric Pyrrole−Imidazole Alkaloids: Sceptrin, Ageliferin, Nagelamide E, Oxysceptrin, Nakamuric Acid, and the Axinellamine Carbon Skeleton

Concepts of Stereoselective Photochemistry and a Case Study: the Paterno-Buchi Reaction

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