A Route to the Thapsigargins from (<i>S</i>)‐Carvone Providing a Substrate‐Controlled Total Synthesis of Trilobolide, Nortrilobolide, and Thapsivillosin F

Oliver, Steven F.; Högenauer, Klemens; Simić, Oliver; Antonello, Alessandra; Smith, Martin D.; Ley, Steven V.

doi:10.1002/anie.200353140

Cited by 110 publications

(58 citation statements)

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“…The system TPAP/NMO/PMS/CH 3 CN is increasingly used [16,64,65], as is TPAP/NMO/PMS/CH 2 Cl 2 -CH 3 CN [52,66]. Various forms of supported TPAP, though not really homogeneous catalysts, have been used to oxidise primary alcohols to aldehydes (cf.…”

Section: Fig 22mentioning

confidence: 99%

“…2.3.3) and including pyranones [144], sialyl alcohols [145], glucals [146], pyrrolidinones [147], bicyclic ketones [148], acetals [149], synthesis of a vinyl oxirane [49], 3-alkylcyclopentenones [150] and hydroxycyclopentene [151]. Examples of lactolto-lactone oxidations effected by TPAP/NMO/PMS/CH 2 Cl 2 include a step for thapsigargin syntheses [152,153], and TPAP/NMO/PMS/CH 3 CN [64] for a tetrol to lactone oxidation [152]. The supported reagent Si-TPAP/O 2 /toluene or supercritical CO 2 /75°C oxidised secondary alcohols to ketones [154]; for oxidations using supported TPAP for secondary and primary alcohols cf.…”

Section: Specific Examplesmentioning

confidence: 99%

“…The reagent TPAP/NMO/PMS/CH 2 Cl 2 was also used in a step in the synthesis of the colony-stimulating factor leustroducsin B (TPAP) [96]; for the antiparasitic spiroketal macrolide (+)-milbemycin a 1 [97]; the antiparasitic insecticide (+)-milbemycin-b 1 (secondary alcohol to a ketone step also) [98]; the sesquiterpenes nortrilobolide, thapsivillosin F and trilobolide (a second step involving the reagent was a lactol-to-lactone transformation) [64]; the marine alkaloid norzoanthamine (secondary alcohol to ketone step also) [99]; the eunicellin ophirin B [84]; the biologically active diterpene phomactin A [100]; the macrolide prelactone B (primary alcohol to lactone) [101]; the spiroketal ionophore antibiotic routiennocin [102,103]; the macrolides salicylihalamides A and B [104]; the anti-tumour microtubulin stablising agents sarcodictyins A and B [105]; the polypropionate siphonarienolone [106]; the antibiotic (+)-tetronomycin [107], and the aglycon of the antitumour antibiotic tetronolide [108]. During synthesis of the protein phosphatase inhibitor okadaic acid three oxidations with TPAP/NMO/PMS/CH 2 Cl 2 were used, two of a primary alcohol to aldehydes and one of a diol to a lactone [109]; the reagent was used in the synthesis of a fragment of the antibiotic sorangicin A [110].…”

Section: Natural Product/pharmaceutical Syntheses Involving Primary Amentioning

confidence: 99%

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Oxidation of Alcohols, Carbohydrates and Diols

Griffith

2009

Catalysis by Metal Complexes

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This is one of the most important classes of oxidation effected by Ru complexes, particularly by RuO 4 , [RuO 4 ] − , [RuO 4 ] 2− and RuCl 2 (PPh 3 ) 3 , though in fact most Ru oxidants effect these transformations. The chapter covers oxidation of primary alcohols to aldehydes (section 2.1), and to carboxylic acids (2.2), and of secondary alcohols to ketones (2.3). Oxidation of primary and secondary alcohol functionalities in carbohydrates (sugars) is dealt with in section 2.4, then oxidation of diols and polyols to lactones and acids (2.5). Finally there is a short section on miscellaneous alcohol oxidations in section 2.6.In this chapter the first of the two most important categories of oxidations catalysed by Ru complexes (the other being alkene and alkyne oxidations in Chapter 3) are considered. The approach in this and subsequent chapters differs from that of Chapter 1, concentrating here on the substrate rather than on the oxidant. The text is divided into the categories of alcohols and their oxidations. There are summaries in section 2.3.6 of systems of limited applicability which are mentioned only in Chapter 1, and in section 2.3.7 of large-scale (>1 g) oxidations.The first oxidations of alcohols by stoicheiometric RuO 4 /H 2 O were reported in 1958, of primary alcohols to aldehydes or carboxylic acids and secondary alcohols to ketones [1]. The first Ru-catalysed oxidation of an alcohol was reported in 1965 when Parikh and Jones used RuO 2 /aq. Na(IO 4 )/CCl 4 1 ( Table 2.3) [2] to oxidise secondary alcohol groups in carbohydrates.Oxidation of alcohols is the most frequently reviewed topic for Ru-catalysed oxidations [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]. Mechanisms of alcohol oxidation by Ru complexes have been reviewed [21].

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Section: Fig 22mentioning

confidence: 99%

Section: Specific Examplesmentioning

confidence: 99%

Section: Natural Product/pharmaceutical Syntheses Involving Primary Amentioning

confidence: 99%

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Oxidation of Alcohols, Carbohydrates and Diols

Griffith

2009

Catalysis by Metal Complexes

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“…[2] These atom-economical processes occur, in most cases, with very high selectivity, and therefore they have been widely used in the total synthesis of many natural products. [3] Although the variety of rearrangement reactions of this type published in the few last years is very broad, probably the most interesting processes are those which imply the formation of a carbonyl compound such as 1 (Scheme 1). Depending on the starting material, these reactions can be divided into two main groups: 1) oxidative rearrangement of olefins 2, [4] and 2) rearrangement of 1,2-difunctionalized compounds 3 (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

IPy₂BF₄‐Mediated Rearrangements of 1,2‐Difunctionalized Compounds and Olefins

Fañanás

Álvarez-Pérez

Rodríguez

2005

Chemistry A European J

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Acetal derivatives are easily obtained from 1,2-difunctionalized compounds by a new reaction mediated by IPy2BF4 with a mechanism based on a 1,2-migration of aryl or alkyl groups. A new oxidative rearrangement reaction of olefins is also described. Moreover, when this metal-free protocol is applied to cyclic olefins, interesting ring-contraction reactions are observed. The new methodologies described here are a clean and efficient alternative to known strategies that make use of potentially toxic metallic complexes.

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“…An extensive review of these sesquiterpenoids encompassing the taxonomy, chemistry, isolation, and structural determination of this interesting class of natural products has been published (3). In this review we reexamine these structures as targets for total synthesis and analog generation in view of their potent biological activity (4).…”

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confidence: 99%