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Review
. 2013 Sep 16;18(9):11384-428.
doi: 10.3390/molecules180911384.

Oxetane synthesis through the Paternò-Büchi reaction

Maurizio D'Auria  1 , Rocco Racioppi
Affiliations
Review

Oxetane synthesis through the Paternò-Büchi reaction

Maurizio D'Auria et al. Molecules. .

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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Figures

Figure 1
Figure 1
Natural and biologically active compounds containing the oxetane ring.
Scheme 1
Scheme 1
The reaction performed by Paternò.
Scheme 2
Scheme 2
Possible mechanisms of the Paternò-Büchi reaction.
Scheme 3
Scheme 3
Reaction of benzophenone with alkenyl sulphide.
Scheme 4
Scheme 4
Reaction of an enol ether.
Scheme 5
Scheme 5
Reaction of 2,3-dihydrofuran.
Scheme 6
Scheme 6
Ring closure of the oxetane ring in the reaction of 2,3-dihydrofuran with acetaldehyde.
Scheme 7
Scheme 7
Possible biradicals in the reactions between 2,3-dihydrofuran and benzaldehyde.
Figure 2
Figure 2
Possible biradical intermediates in the reaction of 2,3-dihydrofuran with benzaldehyde.
Scheme 8
Scheme 8
Ring closure reaction in the formation of the endo isomer of the adduct between 2,3-dihydrofuran and benzaldehyde.
Scheme 9
Scheme 9
Different stereochemical behavior in the reactions of 2,3-dihydrofuran.
Scheme 10
Scheme 10
Metathesis reaction on an oxetane.
Scheme 11
Scheme 11
Reaction of a silyl derivative of cinnamyl alcohol.
Scheme 12
Scheme 12
Reaction of silyl enol ether.
Scheme 13
Scheme 13
Diastereoselectivity in the reaction of a silyl enol ether.
Scheme 14
Scheme 14
Diastereoselectivity in chiral enol silyl ethers reaction with benzaldehyde.
Scheme 15
Scheme 15
Diastereoslectivity on the reaction of some enol ethers.
Figure 3
Figure 3
The conformers (A and B) of the biradical intermediate in the photoreaction between 19 and benzaldehyde.
Scheme 16
Scheme 16
Possible explanation of the observed diastereoselectivity in the reaction of chiral enol ethers.
Scheme 17
Scheme 17
Elaboration on the oxetane ring.
Scheme 18
Scheme 18
The reaction O,S-ketene acetals with carbonyl compound. A possible explanation of the stereochemical behavior.
Scheme 19
Scheme 19
Reacions of N-acyl enamines.
Figure 4
Figure 4
Optimized structure of the biradical intermediate in the reaction of compound 22.
Scheme 20
Scheme 20
Possible explanation of the stereoselctivity observed with N-acyl enamines.
Scheme 21
Scheme 21
Reaction with a chiral enamine.
Scheme 22
Scheme 22
The reaction of 2,5-dimethylthiophene with benzophenone.
Scheme 23
Scheme 23
The reaction of N-methylpyrrole with acetone.
Scheme 24
Scheme 24
Reaction of N-methyl-2-methylimidazole with acetone.
Scheme 25
Scheme 25
The reaction of N-acetylimidazole with benzophenone.
Scheme 26
Scheme 26
Reaction of an isoxazole derivative.
Scheme 27
Scheme 27
Reaction of furan.
Figure 5
Figure 5
Structure of the biradical intermediate in the reaction of furan with benzaldehyde.
Figure 6
Figure 6
Possible biradical intermediates in the reaction of furan with benzaldehyde.
Scheme 28
Scheme 28
Ring closure reaction in the formation of the exo isomer of the adduct between furan and benzaldehyde.
Scheme 29
Scheme 29
Metathesis reactions on oxetanes obtained from furan derivatives.
Scheme 30
Scheme 30
Synthesis of asteltoxin.
Scheme 31
Scheme 31
Reaction of furan with a chiral glyoxylate.
Figure 7
Figure 7
Radical intermediates in the reaction of chiral phenylglyoxylates with furan.
Scheme 32
Scheme 32
The reaction of furan with benzophenone. Conformers of the biradical intermediate.
Scheme 33
Scheme 33
Reaction of allylic alcohol derivatives with benzophenone.
Scheme 34
Scheme 34
Reaction of 2-furylmethanol derivatives.
Scheme 35
Scheme 35
Possible conformations of the biradical intermediate from the reaction of 1-methyl-1-phenyl-1-(2-furyl)methanol with benzaldehyde.
Scheme 36
Scheme 36
Photochemical reaction between DNA pyrimidine derivatives.
Scheme 37
Scheme 37
Reaction of uracil derivative with benzophenone and benzaldehyde.
Scheme 38
Scheme 38
Irradiation of 29.
Scheme 39
Scheme 39
Reaction of homobenzvalene.
Scheme 40
Scheme 40
Esters as carbonyl compounds in the Paternò-Büchi reaction.
Scheme 41
Scheme 41
Reaction of a paracyclophane derivative.
Scheme 42
Scheme 42
Intramolecular oxetane formation in the synthesis of 2,7,9-trimethylenetricyclo[4.3.0.03,8]nonane.
Scheme 43
Scheme 43
Intramolecular oxetane formation on allyl cyclopentanone derivatives.
Scheme 44
Scheme 44
Intramolecular oxetane formation in the reaction of 39.
Scheme 45
Scheme 45
The use of silyl derivatives in the intramolecular synthesis of oxetanes.
Scheme 46
Scheme 46
Chiral intramolecular oxetane synthesis.
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