Photochemical 2 + 2 cycloaddition of arenecarboxylic acid esters to furans and 1,3-dienes. 2 + 2 Cycloreversion of oxetanes to dienol esters and ketones

Cantrell, Thomas S.; Allen, Andrew C.; Ziffer, Herman

doi:10.1021/jo00262a032

Cited by 46 publications

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“…This selectivity has to be confirmed studying the photochemical behavior of other carbonyl compounds, in particular heterocyclic carbonyl compounds. We have only very few data on furan-and thiophene-2-carbaldehyde [42][43][44]. In particular, the possible role of the excited singlet state in this reaction has to be explained, and some heterocyclic aldehydes have a long half-life.…”

Section: Resultsmentioning

confidence: 99%

Regio- and stereoselectivity in the Paternò–Büchi reaction on furan derivatives

D’Auria

Emanuele

Racioppi

2004

Journal of Photochemistry and Photobiology A: Chemistry

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The photochemical coupling reaction between 2,3-dihydrofuran and benzaldehyde was studied by using DFT/B3LYP/6 − 31G + (d, p) method. The regiocontrol of the attack of the benzaldehyde on the double bond is related to the different stabilities of the biradical intermediates. The endo stereoselectivity of the reaction depends on the superposition between HSOMO and LSOMO in the biradical intermediate. In the photochemical reaction between furan and benzaldehyde also the regiocontrol depends on the relative stability of the possible biradical intermediates. The exo stereoselectivity of the coupling reaction depends on the superposition between the HSOMO and LSOMO of the biradical intermediate. The reaction of chiral phenylglyoxylates with furan gave the corresponding adducts with de = 15-95%. The stereocontrol 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. The reaction of benzoin and 2-phenylpropiophenone with furan gave the cycloadduct with high diastereocontrol. All the products were obtained with de > 98%. The Paterrnò-Büchi reaction between 2-furylmethanols with aromatic carbonyl compounds also showed high regio-and stereocontrol. On the contrary, when 5-methyl derivatives were used, a lack of regiocontrol was observed. Furthermore, with aliphatic carbonyl compounds, no diastereoselectivity was observed. These results were explained assuming the attack of the excited carbonyl compound on the same side as the hydroxyl group, through the formation of a hydrogen bond or of a complex. This type of attack gave the biradical intermediate in preferential conformations. The relative energies of these conformers account for the observed diastereoselectivity.

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Section: Resultsmentioning

confidence: 99%

Regio- and stereoselectivity in the Paternò–Büchi reaction on furan derivatives

D’Auria

Emanuele

Racioppi

2004

Journal of Photochemistry and Photobiology A: Chemistry

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“…In this case, the adducts can be obtained in a few cases. In most of the examples, they underwent a cycloreversion reaction to give the ring opening products (Scheme 29) [153]. More recently, this result has been questioned and a 95:5 mixture of stereoisomeric adducts was identified as the product [148].…”

Section: Reactions With Heterocyclic Compoundsmentioning

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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“…10 Only about 5% of petroleum is used as feedstock for petrochemicals. 11 Given the global depletion of petroleum resources, a rational decision would be to conserve these hydrocarbons for the manufacture of petrochemical products in lieu of burning them for fuel. 12,13 An attractive alternative energy source is natural gas, as burning natural gas produces less pollutants and less CO 2 than does burning petroleum.…”

Section: Chemicals From Natural Gas and Petroleummentioning

confidence: 99%

“…10 Also, a metal-coordinated tris(pyrazolyl)alkane has even been observed with a naked carbanion backbone. 11 The study of poly(pyrazolyl)alkanes as ligands is not as well developed as for the poly(pyrazolyl)borate variants due in part to synthetic challenges (including moderate to low yields and multi-step isolation procedures); nevertheless, progress is being made towards greater use of this class of ligand, 3,6,9 particularly for their use in the synthesis of Cu(II)-selective membrane electrodes, 12 Re complexes for diagnostic purposes, 7 and as scaffold ligands for successful Ru(II) ethylene hydrophenylation catalysts. 13 In fact, the use of…”

Section: Introductionmentioning

confidence: 99%

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The Development of Ru(II) and Fe(II) Complexes for C-H and H2 Bond Activation

Taylor

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Hydrocarbons serve as the feedstocks for numerous commodity chemicals. Industrial methods to functionalize hydrocarbons in order to convert them into higher value chemicals often involve cost and energy intensive processes. Furthermore, these processes often do not provide high selectivity for the desired products. Thus, the development of a catalytic method to functionalize hydrocarbons with high selectivity and under mild reaction conditions is highly attractive. C-H bond activation, the breaking of a substrate's C-H bond, is a vital step in hydrocarbon functionalization. The work described in this thesis involves the development and

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Photochemical 2 + 2 cycloaddition of arenecarboxylic acid esters to furans and 1,3-dienes. 2 + 2 Cycloreversion of oxetanes to dienol esters and ketones

Cited by 46 publications

References 0 publications

Regio- and stereoselectivity in the Paternò–Büchi reaction on furan derivatives

Regio- and stereoselectivity in the Paternò–Büchi reaction on furan derivatives

Oxetane Synthesis through the Paternò-Büchi Reaction

The Development of Ru(II) and Fe(II) Complexes for C-H and H2 Bond Activation

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