Photochemical Synthesis of Oxetans

Carless, H. A. J.

doi:10.1007/978-1-4613-2681-6_8

Cited by 41 publications

(4 citation statements)

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“…A [2 + 2] cycloaddition of π-electron compounds is potentially an attractive, straightforward way for obtaining the four-membered heterocycles (Scheme ) . The ketene [2 + 2] cycloaddition (dimerization), which serves as a kind of reference reaction in this paper, has been studied by both experimental and theoretical , methods. In 1934, kinetic studies revealed that diketene dimerization does not proceed through a biradical intermediate 10a.…”

Section: Introductionmentioning

confidence: 99%

Reaction Paths of the [2 + 2] Cycloaddition of XCY Molecules (X, Y = S or O or CH₂). Ab Initio Study

Rode

Dobrowolski

2005

J. Phys. Chem. A

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The reaction paths of [2+2] cycloaddition of the X=C=Y cumulenes were modeled at the MP2/aug-cc-pVDZ level. Cycloadditions of allene and CO2, CS2, or OCS lead in part to the same four-membered products as dimerizations of either ketene or thioketene or addition of ketene and thioketene, respectively. All the reactions studied are concerted and mostly asynchronous. The majority of the allene cycloadditions studied are endoergic and proceed with much higher activation barriers than do the alternative (thio)ketene additions. In comparison with the energy of the substrates, the four-membered cycles incorporating S-atoms are stabilized more than the analogous structures with O-atoms built into the rings. There are also some products that are thermodynamically disfavored, yet seem to be obtainable thanks to a relatively low barrier of the reaction. The AIM analysis of the electron density distribution in the transition state structures allowed distinguishing pericyclic from pseudopericyclic and nonplanar-pseudopericyclic types of reaction.

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Section: Introductionmentioning

confidence: 99%

Reaction Paths of the [2 + 2] Cycloaddition of XCY Molecules (X, Y = S or O or CH₂). Ab Initio Study

Rode

Dobrowolski

2005

J. Phys. Chem. A

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“…1,2 After these pioneering works, several reviews cover the enormous number of papers published in this field. [3][4][5][6][7] The Paternò-Büchi reaction is a photocycloaddition reaction of a n,π* carbonyl compound to an alkene in the ground state from either the S 1 or the T 1 state. The reaction can occur through the initial formation of a C-O bond or through the formation of a C-C bond.…”

Section: Introductionmentioning

confidence: 99%

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

D’Auria

Emanuele

Racioppi

2003

Photochem Photobiol Sci

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The reaction of (S)-1-methylpropylbenzoylformate with furan gave (1'S)-1'-methylpropyl (1S,5R,6R)-6alpha-phenyl-2,7-dioxabicyclo[3.2.0]hept-3-en-6beta-carboxylate with de = 15%. The reaction of (S)-2-methylbutyl benzoylformate with furan gave (2'S)-2-methylbutyl (1SR,5RS,6RS)-6alpha-phenyl-2,7-dioxabicyclo[3.2.0]hept-3-en-6beta-carboxylate as a mixture of stereoisomers. (1R,2S,5R)-5-Methyl-2-(1-methylphenylethyl)cyclohexyl benzoylformate gave (1R,2S,5R)-5-methyl-2-(1-methylphenylethyl)cyclohexyl (1R,5S,6S)-6alpha-phenyl-2,7-dioxabicyclo[3.2.0]hept-3-en-6beta-carboxylate with de = 95%. The stereochemical behaviour can be explained considering the energy gap between the biradical intermediates in the coupling reaction. When the reaction was performed in the presence of zeolite, the diastereoisomeric excess increased (37, 18 and 98%, respectively). The reaction of (S)-1-methylpropylbenzoylformate with 2-methylfuran gave (1'S)-1'-methylpropyl (1S,5R,6R)-1-methyl-6alpha-phenyl-2,7-dioxabicyclo[3.2.0]hept-3-en-6beta-carboxylate (yield: 12%) with de = 94%. The main product was (1'S)-1'-methylpropyl (1SR,5RS,6RS)-3-methyl-6alpha-phenyl-2,7-dioxabicyclo[3.2.0]hept-3-en-6beta-carboxylate as a mixture of diastereoisomers. The reaction of (S)-2-methylbutyl benzoylformate with 2-methylfuran gave (2'S)-2-methylbutyl (1S,5R,6R)-1-methyl-6alpha-phenyl-2,7-dioxabicyclo[3.2.0]hept-3-en-6beta-carboxylate (yield: 9%) with de = 10%. The main product was (2'S)-2-methylbutyl (1SR,5RS,6RS)-3-methyl-6alpha-phenyl-2,7-dioxabicyclo[3.2.0]hept-3-en-6beta-carboxylate as a mixture of stereoisomers. The stereochemical behaviour can be explained on the basis of the energy gap between the possible biradical intermediates. The reaction of (S)-1-methylpropylbenzoylformate and (S)-2-methylbutyl benzoylformate with 2-furylmethanol gave the corresponding adducts as a mixture of diastereoisomers. The reaction of (S)-1-methylpropylbenzoylformate and (S)-2-methylbutyl benzoylformate with 2-furylphenylmethanol gave the corresponding adducts with high diastereoselectivity. In this case, the stereochemical behaviour is determined by the presence of the hydroxy group in a molecule with a preferntial conformation.

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“…The Paternò-Büchi reaction can also be applied to other unsaturated systems other than alkenes, such as dienes [10], allenes [236], acetylenes [237], and ketenimines [236]. When tetramethylallene reacted with aromatic ketones the main products resulted from bis-addition of the carbonyl compounds to give dioxaspiroheptanes [238,239].…”

Section: Other Intermolecular Reactionsmentioning

confidence: 99%

“…Only in 1953 Büchi reported the exact identification of the product, showing that this photochemical reaction could represent an interesting synthetic process [7]. After these pioneering works, several reviews have covered the relevant papers published in this field [8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24].…”

Section: Introductionmentioning

confidence: 99%

Oxetane Synthesis through the Paternò-Büchi Reaction

D’Auria

Racioppi

2013

Molecules

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Abstract:The Paternò-Büchi reaction is a photochemical reaction between a carbonyl compound and an alkene to give the corresponding oxetane. In this review the mechanism of the reaction is discussed. On this basis the described use in the reaction with electron rich alkenes (enolethers, enol esters, enol silyl ethers, enanines, heterocyclic compounds has been reported. The stereochemical behavior of the reaction is particularly stressed. We pointed out the reported applications of this reaction to the synthesis of naturally occuring compounds.

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Photochemical Synthesis of Oxetans

Cited by 41 publications

References 239 publications

Reaction Paths of the [2 + 2] Cycloaddition of XCY Molecules (X, Y = S or O or CH₂). Ab Initio Study

Reaction Paths of the [2 + 2] Cycloaddition of XCY Molecules (X, Y = S or O or CH₂). Ab Initio Study

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

Oxetane Synthesis through the Paternò-Büchi Reaction

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Photochemical Synthesis of Oxetans

Cited by 41 publications

References 239 publications

Reaction Paths of the [2 + 2] Cycloaddition of XCY Molecules (X, Y = S or O or CH2). Ab Initio Study

Reaction Paths of the [2 + 2] Cycloaddition of XCY Molecules (X, Y = S or O or CH2). Ab Initio Study

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

Oxetane Synthesis through the Paternò-Büchi Reaction

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Reaction Paths of the [2 + 2] Cycloaddition of XCY Molecules (X, Y = S or O or CH₂). Ab Initio Study

Reaction Paths of the [2 + 2] Cycloaddition of XCY Molecules (X, Y = S or O or CH₂). Ab Initio Study