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The oxidative conversion of alicyclic ketones into lactones with permonosulfuric acid was discovered by Baeyer and Villiger in 1899, and in their honor the general process by which ketones are converted into esters or lactones is now known as the Baeyer–Villiger reaction. The literature on this synthetically useful process has been reviewed comprehensively through 1953 in Volume 9 of Organic Reactions , and less comprehensive reviews of the reaction have appeared since then. More recent investigations have led to the development of new synthetic reagents, to improvements in experimental reaction conditions, and to a better understanding of regiochemical and stereochemical aspects of the reaction. Baeyer–Villiger reactions now often can be carried out with functional group chemoselectivity and regiochemical control. Although the recent removal from commerce of 90% hydrogen peroxide and reagents based upon this oxidant are a setback to Baeyer–Villiger reaction methodology, alternative reagents, catalysts, and methods described in this review are available to fill the gaps. The definition of the Baeyer–Villiger reaction is somewhat fuzzy, and can be considered to include both ketones and aldehydes. In addition to the traditional use of organic and inorganic peracids as oxidants, examples of oxygen insertion reactions using hydrogen peroxide, alkyl peroxides, and several metal ion oxidants are considered to fall within the scope of this chapter and are included in the tabular survey.
The oxidative conversion of alicyclic ketones into lactones with permonosulfuric acid was discovered by Baeyer and Villiger in 1899, and in their honor the general process by which ketones are converted into esters or lactones is now known as the Baeyer–Villiger reaction. The literature on this synthetically useful process has been reviewed comprehensively through 1953 in Volume 9 of Organic Reactions , and less comprehensive reviews of the reaction have appeared since then. More recent investigations have led to the development of new synthetic reagents, to improvements in experimental reaction conditions, and to a better understanding of regiochemical and stereochemical aspects of the reaction. Baeyer–Villiger reactions now often can be carried out with functional group chemoselectivity and regiochemical control. Although the recent removal from commerce of 90% hydrogen peroxide and reagents based upon this oxidant are a setback to Baeyer–Villiger reaction methodology, alternative reagents, catalysts, and methods described in this review are available to fill the gaps. The definition of the Baeyer–Villiger reaction is somewhat fuzzy, and can be considered to include both ketones and aldehydes. In addition to the traditional use of organic and inorganic peracids as oxidants, examples of oxygen insertion reactions using hydrogen peroxide, alkyl peroxides, and several metal ion oxidants are considered to fall within the scope of this chapter and are included in the tabular survey.
Eingegangen a m 19. April 1968 I -Morpholino-cyclohexen-( I) reagiert mit Zimtaldehyd zu 2-Morpholino-4-phenyl-bicyclo-[3.3. I]nonanon-(9) (l), wobei das nicht isolierte Diels-Alder-Zwischenprodukt 14 entsteht. Dabei werden erstmals drei der vier moglichen Stereoisomeren von 1 (a-d) erhalten, deren Stereochemie durch Abbau und Umlagerung zum aquatorialen 2-Phenyl-bicyclo[3.3.1 Inonan (5b) geklart wird. Umsetzung von Morpholino-cyclohexen mit ZimtaldehydZimtaldehyd und Morpholino-cyclohexen reagieren in Benzol oder Toluol unter Addition mit 70--80% d.Th. zu den drei isomeren 2-Morpholino-4-phenyl-bicyclo-[3.3.l]nonanonen-(9) l acl), die im Verhaltnis 10: 1 : 0.5 entstehen. Das vermutete vierte Isomere (1 d) konnte nicht sicher nachgewiesen werden.Die Kondensation von Zimtaldehyd mit Morpholino-cyclohexen unter Bildung von nur einem Reaktionsprodukt, das offenbar verunreinigtes 1 a darstellt, ist beschriebenz).Bei der Aufarbeitung mit verdiinnter Salzsaure/Isopropylalkohol bleibt das Hydrochlorid von 1 b groBtenteils gelost, wahrend die Hydrochloride von l a und c ausfallen.Die Trennung von l a und l c beruht auf der verschiedenek Loslichkeit der Hydrochloride in Wasser oder waRr. Athanol: Das Hydrochlorid von l c ist darin schwerer Ioslich; die Base 1 c lost sich in Isopropylalkohol leichter. Die Trennungen wurden diinnschichtchromatographisch verfolgt.Die Ausbeuten und das Verhaltnis von a : b : c schwanken bei verschiedenen Ansatzen; Siurekatalyse scheint die Gesamt-Ausbeute zu begiinstigen.
Synthesis and Structure of Phenyl-Substituted Bicyc10[3.3.1]nonenes~~~Addition of one mole of phenyllithium to bicyclo[3.3.l]nonane-2,6-dione (5) affords the hydroxy ketone 6 besides small amounts of the known diol7. Dehydration of this mixture by sulfuric acid in acetic acid yields the unsaturated ketone 8 and the diene 1 which are separated by chromatography. Wolff-Kishner reduction of 8 furnished the hydrocarbon 2. In the same way, the known ketones exo-and endo-10 are converted into 4. The preferential formation of the less stable endo-10 is interpreted in terms of the relative stability of the conformations required in the intramolecular aldol reaction of diketone 9. The conformations of 4, 8, exo-and endo-10 are determined by X-ray diffraction analyses. Vicinal proton coupling constants are calculated from torsional angles and compared to those determined in solutions by high-field NMR spectroscopy.Wir fanden kurzlich, daB die symmetrisch substituierten Di- Das Ubenviegen des endo-Diastereomers endo-10 bei der Cyclisierung liegt wohl nicht an der relativen Stabilitat der diastereomeren Vorstufen u-und 1-9, da diese unter den Reaktionsbedingungen leicht durch Epimerisierung der a-Stellung des Cyclohexanon-Rings ineinander umgewandelt werden durften. Vielmehr laBt sich die Bevorzugung von endo-10 durch Betrachtung der beiden diastereomeren, zu den Ubergangszustanden der intramolekularen Aldol-Addition fiihrenden Konformationen von u-und 1-9 verstehen, in denen die
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