A General Oxidative Cyclization of 1,5‐Dienes Using Catalytic Osmium Tetroxide

Donohoe, Timothy J.; Butterworth, Sam

doi:10.1002/anie.200390253

Cited by 89 publications

(25 citation statements)

References 22 publications

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“…The Donohoe group presented a total synthesis in 2003 using an Os(VIII)-catalyzed oxidative cyclization as the key step [31] (Scheme 4). Several other total syntheses of that natural product did already exist or followed [32–39].…”

Section: Reviewmentioning

confidence: 99%

“…Thus, mono-protection of THF diol 5 followed by oxidation of the remaining free primary hydroxy group to the carboxylic acid and a final hydrogenolysis gave (+)-D-chitaric acid ( 7 ) with a yield of 30% over three steps (Scheme 4). Additional to the synthesis of Donohoe described above [31], two other total syntheses of (+)-D-chitaric acid have been reported [40–41]. …”

Section: Reviewmentioning

confidence: 99%

“…This reaction has been reported to be catalyzed by Os(VI), Ru(VII) and Cr(VI) [24–26] and can be termed type B oxidative cyclization (as opposed to the direct oxidative cyclization of 1,5-dienes, referred to as type A reaction; cf. Scheme 3).…”

Section: Introductionmentioning

confidence: 99%

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The direct oxidative diene cyclization and related reactions in natural product synthesis

Adrian¹,

Gross²,

Stark³

2016

Beilstein J. Org. Chem.

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SummaryThe direct oxidative cyclization of 1,5-dienes is a valuable synthetic method for the (dia)stereoselective preparation of substituted tetrahydrofurans. Closely related reactions start from 5,6-dihydroxy or 5-hydroxyalkenes to generate similar products in a mechanistically analogous manner. After a brief overview on the history of this group of transformations and a survey on mechanistic and stereochemical aspects, this review article provides a summary on applications in natural product synthesis. Moreover, current limitations and future directions in this area of chemistry are discussed.

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Section: Reviewmentioning

confidence: 99%

Section: Reviewmentioning

confidence: 99%

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The direct oxidative diene cyclization and related reactions in natural product synthesis

Adrian¹,

Gross²,

Stark³

2016

Beilstein J. Org. Chem.

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“…Early transition metals catalyze oxidation of alkenols bearing two alkyl groups at the terminal alkene carbon, providing in reactions with tert-butyl hydroperoxide (TBHP) 2,3-cis-, 2,4-trans-, and 2,5-cis-(tetrahydrofuran-2-yl)alkanols in synthetically useful selectivity [15]. High valent, fourth-to fifth-row late-transition metal oxo compounds oxidize the same type of substrates with complementary stereoselectivity [25][26][27][28][29][30]. Oxidizing alkenols with carbohydrate-derived dioxiranes [31][32][33][34] furnishes for a structurally narrow range of alkenols enantiomerically enriched epoxy alcohols, which rearrange to tetrahydrofuranyl-2-methanols, when treated with a Brønsted-acid [35].…”

Section: Introductionmentioning

confidence: 99%

Activating tert-butyl hydroperoxide by chelated vanadates for stereoselectively preparing sidechain-functionalized tetrahydrofurans

Dönges

Amberg

Niebergall

et al. 2015

Journal of Inorganic Biochemistry

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“…Since the initial report by Klein and Rojahn a variety of other metal-oxo species have been shown to accomplish this transformation with varying degrees of competency [5][6][7]. We have reported the development of the oxidative cyclization of 1,5-dienes, through the employment of catalytic Os(VI) under acidic conditions [8], in the presence of a tertiary amine N-oxide [for the reoxidation of Os(IV) to Os(VI)], to form exclusively cis-THFs in high yields [9]. During further investigations we have disclosed a significant improvement to the original methodology with the realization that vicinal diols, possessing a pendent olefin moiety, will form the THF products when subjected to oxidative cyclization conditions (Scheme 1) [10].…”

Section: Introductionmentioning

confidence: 99%

Oxidative cyclization for the synthesis of complex tetrahydrofuran-containing natural products

Pullin

Lipiński

Donohoe

2013

Pure and Applied Chemistry

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The osmium-catalyzed oxidative cyclization of vicinal diols onto proximal olefins to generate 2,5-cis-substituted tetrahydrofurans (THFs) has been exploited as the key step for the construction of several complex THF-containing natural products, namely, the annonaceous acetogenins cis-sylvaticin, sylvaticin, and the excitatory amino acid neodysiherbaine A. Recently modified conditions that employ a Lewis acid enable the cyclization to proceed under milder conditions, providing greater tolerance to acid-sensitive functional groups, as demonstrated in two of the syntheses. Flexibility for the construction of 2,5-trans-THFs was demonstrated in the synthesis of sylvaticin by utilization of an intramolecular hydride-shift sequence.Scheme 1 Osmium-catalyzed oxidative cyclization for the diastereoselective synthesis of cis-THFs and pyrrolidines. Scheme 6Hydride shift-intramolecular trapping for the synthesis of the trans-THF ring of sylvaticin.Scheme 7 Synthesis of the butenolide fragments: 26 for cis-sylvaticin and 24 for sylvaticin. Brought to you by | West Virginia University Authenticated Download Date | 11/19/14 6:26 PM 25. Necessary removal of the TBS group of 25 was then undertaken, by treatment with AcCl in MeOH, to afford 26.The end-game for the syntheses involved the union of the bis-THF and butenolide fragments, which in each case was achieved by CM (Scheme 8). For cis-sylvaticin, CM of bis-THF 9, using Grubbs II catalyst with 4 equiv of 26 (in order to avoid homodimerization of 9; the homodimer of 26 could be recovered and recycled into the reaction), gave the desired CM product 27 in good yield (79 %). The synthesis was completed in two final steps via diimide reduction of the disubstituted alkene and global removal of the three silyl protecting groups, thus completing the first total synthesis of cis-sylvaticin (2) in only 13 linear steps [24]. In a similar manner, for sylvaticin, CM of 16, using Grubbs-Hoveyda II and 24 (4 equiv), gave the CM product 28 in good yield (84 %). Conclusion of the synthesis, in line with that shown for cis-sylvaticin, gave sylvaticin (1), which again completed the first synthesis of the natural product via a 19-step linear sequence. In both cases the synthesis confirmed the structure of the natural products as originally reported by McLaughlin. NEODYSIHERBAINE ANeodysiherbaine A (29) is an excitatory amino acid, first isolated in 2001 by Sakai and co-workers from the Micronesian marine sponge Dysidea herbacea [25]. Neodysiherbaine A was found to be a potent convulsant and a highly selective agonist for kainate (KA) and α-amino-3-hydroxy-5-methyl-4-isoxazole propionate (AMPA) glutamate receptors [26]. The first total synthesis was accomplished by Sakai in 26 steps [25], and three subsequent syntheses have been reported, which ranged between 15 to 23 R. D. C. PULLIN et al. Scheme 11Construction of the carbon skeleton via Negishi coupling.Scheme 12 Formation of the bicyclic core of neodysiherbaine A via oxidative cyclization.

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A General Oxidative Cyclization of 1,5‐Dienes Using Catalytic Osmium Tetroxide

Cited by 89 publications

References 22 publications

The direct oxidative diene cyclization and related reactions in natural product synthesis

The direct oxidative diene cyclization and related reactions in natural product synthesis

Activating tert-butyl hydroperoxide by chelated vanadates for stereoselectively preparing sidechain-functionalized tetrahydrofurans

Oxidative cyclization for the synthesis of complex tetrahydrofuran-containing natural products

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