Oxidation of alcohols using benzeneseleninic anhydride

Barton, Derek H. R.; Brewster, Andrew G.; Hui, R.; Lester, David; Ley, Steven V.; Back, Thomas G.

doi:10.1039/c39780000952

Cited by 59 publications

(32 citation statements)

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“…[1] The use of aromatic diselenide-based oxidation catalysts was first reported in 1978, [2] and these reagents have subsequently been shown to be versatile and selective catalysts in a number of oxidative transformations. [3] Among other reactions, they catalyze the oxidation of alcohols, albeit with generally high catalyst loadings ( Figure 1).…”

Section: Introductionmentioning

confidence: 99%

Studies on Substituted Aromatic Diselenides as Catalysts for Selective Alcohol Oxidation Using tert‐Butyl Hydroperoxide

et al. 2011

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We have investigated the Ph2Se2‐catalysed oxidation of alcohols with tert‐butyl hydroperoxide (TBHP) by using a variety of spectroscopic techniques and reaction calorimetry. We showed that the active oxidant is benzeneseleninic anhydride (BSA), formed by reaction of Ph2Se2 with TBHP. The influence of aromatic substituents on the activity of a selection of nine aromatic diselenides involved in alcohol oxidations was studied. Calorimetric experiments showed that compounds that are activated more rapidly have higher initial activity in the catalytic oxidation of benzyl alcohol. An exception to this rule was observed when the diselenide contained a dimethylamino group in the ortho position, which can apparently compensate for its slow pre‐activation by a special ortho effect. An aliphatic alcohol, 1‐decanol was also used as a substrate. Besides diphenyl diselenide only three of the substituted diaryl diselenides studied showed reasonable activity after pre‐activation with TBHP. Dimesityl diselenide displayed the highest activity and selectivity for the oxidation of 1‐decanol. Specificity for a given aldehyde could be achieved by using an oxidant and substrate feed protocol.

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Section: Introductionmentioning

confidence: 99%

Studies on Substituted Aromatic Diselenides as Catalysts for Selective Alcohol Oxidation Using tert‐Butyl Hydroperoxide

et al. 2011

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“…11 und 12 treten dabei als Nebenprodukte in variabler Ausbeute auf, und ihre Abtrennung durch mehrfache Chromatographie ist schwierig. Deutlich besser verlauft die Oxidation rnit Benzolseleninsaureanhydrid (BSA) in Benzo12',22) Offensichtlich hat die raumlich benachbarte Carboxyl-Gruppe in 22 einen wesentlichen EinfluR auf den Verlauf der Nitrierung. Auch rnit anderen Reagenzien, wie Cu(1I)-nitrat3*), HN0339) und 2,3,5,6-Tetrabrom-4-methyl-4-nitro-2,5-cyclohexadienon 40) konnte kein definiertes Produkt erhalten werden.…”

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Synthese von (+)‐Taxodion

Haslinger

Michl

1989

Liebigs Ann. Chem.

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+)-Taxodion (l), ein Diterpen rnit Abietan-Skelett, wurde aus Taxodium distichum (L.) Rich. (Taxodiaceae) isoliert ' ,*I und ist ein sehr wirkungsvoller Tumorinhibitor ' I. Deshalb, aber auch wegen seiner interessanten Struktur als Chinonmethid hat sich eine Reihe von Arbeitsgruppen rnit der Synthese von 2 befa13t4-'3). Da die bisher beschriebenen Synthesen nicht ergiebig sind, haben wir eine entwickelt, die es gestattet, 1 in recht guter Gesamtausbeute stereoselektiv aus ( -)-Abietinsaure (2) herzustellen.

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“…In addition, it was noteworthy that the hydroxymethyl group of 11 was converted into the ether 16 by oxidative cyclization when it was treated with benzeneselenic anhydride. 50 The ether, dehydro-16-epinormacusine B ( 16 ), had been previously prepared by DDQ-mediated oxidative cyclization. 31 A potential mechanism of oxidation of indole 11 to provide ether 16 is illustrated in Scheme 3.…”

Section: Resultsmentioning

confidence: 99%

“…The hydroxymethyl group which remained was converted into the methyl ester 35 via the 2 steps detailed below. Various oxidative reagents (i.e., TPAP, 69 Dess-Martin periodinate, 44 and benzeneselenic anhydride 50 ) were employed to furnish the equatorial aldehyde 36 ; however, most of these efforts resulted in the decomposition of the starting material or cleavage of the C(6)–C(17)-oxygen bridge. Again, the conditions of the Corey-Kim oxidation could be employed successfully in this system; the monol 34 was converted into the equatorial aldehyde 35 in 90% yield.…”

Section: Resultsmentioning

confidence: 99%

Enantiospecific Total Synthesis of the Important Biogenetic Intermediates along the Ajmaline Pathway, (+)-Polyneuridine and (+)-Polyneuridine Aldehyde, as well as 16-Epivellosimine and Macusine A

et al. 2010

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The first stereospecific synthesis of polyneuridine aldehyde (6), 16-epi-vellosimine (7), (+)-polyneuridine (8), and (+)-macusine A (9) has been accomplished from commercially available D-(+)-tryptophan methyl ester. D-(+)-Tryptophan has served here both as the chiral auxiliary and the starting material for the synthesis of the common intermediate, (+)-vellosimine (13). This alkaloid was available in enantiospecific fashion in seven reaction vessels in 27% overall yield from D-(+)-trytophan methyl ester (14) via a combination of the asymmetric Pictet-Spengler reaction, Dieckmann cyclization, and a stereocontrolled intramolecular enolate-driven palladium-mediated cross-coupling reaction. A new process for this stereocontrolled intramolecular cross-coupling has been developed via a copper-mediated process. The initial results of this investigation indicated that an enolate driven palladium-mediated cross-coupling reaction can be accomplished by a copper-mediated process which is less expensive and much easier to work-up. An enantiospecific total synthesis of (+)-polyneuridine aldehyde (6), which has been proposed as an important biogenetic intermediate in the biosynthesis of quebrachidine (2), was then accomplished in an overall yield of 14.1% in 13 reaction vessels from D-(+)-tryptophan methyl ester (14). Aldehyde 13 was protected as the Na-Boc aldehyde 32 and then converted into the prochiral C (16)-quaternary diol 12 via the practical Tollens’ reaction and deprotection. The DDQ-mediated oxidative cyclization and TFA/Et3SiH reductive cleavage served as protection/deprotection steps to provide a versatile entry into the three alkaloids, polyneuridine aldehyde (6), polyneuridine (8) and macusine A (9) from the quarternary diol 12. The oxidation of the 16-hydroxymethyl group present in the axial position was achieved with the Corey-Kim reagent to provide the desired β-axial aldehydes, polyneuridine aldehyde (6) and 16-epi-vellosimine (7) with 100% diastereoselectivity.

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Oxidation of alcohols using benzeneseleninic anhydride

Cited by 59 publications

References 0 publications

Studies on Substituted Aromatic Diselenides as Catalysts for Selective Alcohol Oxidation Using tert‐Butyl Hydroperoxide

Studies on Substituted Aromatic Diselenides as Catalysts for Selective Alcohol Oxidation Using tert‐Butyl Hydroperoxide

Synthese von (+)‐Taxodion

Enantiospecific Total Synthesis of the Important Biogenetic Intermediates along the Ajmaline Pathway, (+)-Polyneuridine and (+)-Polyneuridine Aldehyde, as well as 16-Epivellosimine and Macusine A

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