Dehydrogenation with benzeneseleninic anhydride in the total synthesis of ergot alkaloids

Ninomiya, Ichiya; Hashimoto, Chiyomi; Kiguchi, Toshiko; Naito, Takeaki; Barton, Derek H. R.; Lusinchi, X.; Milliet, P.

doi:10.1039/p19900000707

Cited by 40 publications

(17 citation statements)

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“…ConcentrationS15under pressure gave an oily residue, which was purified by PTLC with EtOAc-MeOH (3:1) to give isolysergol 3 as a pale brown solid (3.8 mg, 99% yield): IR (neat): 3213 (OH), 1604 (C=C), The IR spectra was found to be identical with that of natural isolysergol. 4 1 H NMR (500 MHz, CDCl 3 -CD 3 OD) δ 2.44-2.50 (m, 1H), 2.55 (s, 3H), 2.65 (ddd, J = 14.3, 11.5, 1.7 Hz, 1H), 2.85 (ddd, J = 11.5, 4.0, 1.7 Hz, 1H), 3.04 (d, J = 11.5 Hz, 1H), 3.14-3.19 (m, 1H), 3.53 (dd, J = 14.3, 5.7 Hz, 1H), 3.80 (ddd, J = 10.3, 3.6, 1.7 Hz, 1H), 3.96 (dd, J = 10.3, 3.4 Hz, 1H), 6.46 (d, J = 5.7 Hz, 1H),6.89 (d, J = 1.7 Hz, 1H), 7.14-7.17 (m, 2H), 7.18-7.22 (m, 1H); The 1 H NMR spectra was found to be identical with that of synthesized isolysergol reported by Ninomiya and Naito 5. 13 C NMR (125 MHz, CDCl 3 -CD 3 OD) δ 27.3, 36.3, 43.3, 57.4, 63.0, 66.0, 109.5, 109.9, 111.7, 118.2, 121.0, 122.9, 126.0, 128.0, 133.8, 136.7; HRMS (FAB) calcd C 16 H 17 N 2 O: [M -H] -, 253.1346; found: [M -H] To a stirred solution of S4b (16.7 mg, 0.030 mmol) in THF (0.7 mL) was added TBAF (1.00 M solution in THF; 39 μL, 0.039 mmol) at 0 °C.…”

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confidence: 78%

Total Synthesis of (±)-Lysergic Acid, Lysergol, and Isolysergol by Palladium-Catalyzed Domino Cyclization of Amino Allenes Bearing a Bromoindolyl Group

et al. 2008

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confidence: 78%

Total Synthesis of (±)-Lysergic Acid, Lysergol, and Isolysergol by Palladium-Catalyzed Domino Cyclization of Amino Allenes Bearing a Bromoindolyl Group

et al. 2008

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“…While benzeneseleninic anhydride is not the same as SeO 2 , owing to the remarkable observations of Barton and coworkers, one set of examples is included. Barton and co-workers found the reaction of 17 and benzeneseleninic anhydride afforded 18 in 42% yield and the 2-selenide derivative 19 in 20% yield [24]. The addition of 3.0 equiv of indole (20) as a scavenger for Se(II) caused formation of 18 in almost quantitative yield, the complete absence of the unwanted derivative 19, and the formation of the indole-trapped phenylselenide 21 (Scheme 3).…”

Section: Diverse Conditions For the Riley Oxidationmentioning

confidence: 99%

Riley Oxidation of Heterocyclic Intermediates on Paths to Hydroporphyrins—A Review

Wang

Lindsey

2020

Molecules

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Riley oxidation of advanced heterocyclic intermediates (dihydrodipyrrins and tetrahydrodipyrrins) is pivotal in routes to synthetic hydroporphyrins including chlorins, bacteriochlorins, and model (bacterio)chlorophylls. Such macrocycles find wide use in studies ranging from energy sciences to photomedicine. The key transformation (–CH3 → –CHO) is often inefficient, however, thereby crimping the synthesis of hydroporphyrins. The first part of the review summarizes 12 representative conditions for Riley oxidation across diverse (non-hydrodipyrrin) substrates. An interlude summarizes the proposed mechanisms and provides context concerning the nature of various selenium species other than SeO2. The second part of the review comprehensively reports the conditions and results upon Riley oxidation of 45 1-methyltetrahydrodipyrrins and 1-methyldihydrodipyrrins. A comparison of the results provides insights into the tolerable structural features for Riley oxidation of hydrodipyrrins. In general, Riley oxidation of dihydrodipyrrins has a broad scope toward substituents, but proceeds in only modest yield. Too few tetrahydrodipyrrins have been examined to draw conclusions concerning scope. New reaction conditions or approaches will be required to achieve high yields for this critical transformation in the synthesis of hydroporphyrins.

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“…Oxidation of indolines affords the corresponding indoles, and this method was successfully applied to the final step in total synthesis of ergot alkaloids, among them (±)-lysergol 55 (Scheme 21) [139].…”

Section: Organoselenium Compounds As Oxidizing Agents and Oxidatiomentioning

confidence: 99%

Developments in Synthetic Application of Selenium(IV) Oxide and Organoselenium Compounds as Oxygen Donors and Oxygen-Transfer Agents

2015

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A variety of selenium compounds were proven to be useful reagents and catalysts for organic synthesis over the past several decades. The most interesting aspect, which emerged in recent years, concerns application of hydroperoxide/selenium(IV) oxide and hydroperoxide/organoselenium catalyst systems, as "green reagents" for the oxidation of different organic functional groups. The topic of oxidations catalyzed by organoselenium derivatives has rapidly expanded in the last fifteen years This paper is devoted to the synthetic applications of the oxidation reactions mediated by selenium compounds such as selenium(IV) oxide, areneseleninic acids, their anhydrides, selenides, diselenides, benzisoselenazol-3(2H)-ones and other less often used other organoselenium compounds. All these compounds have been successfully applied for various oxidations useful in practical organic syntheses such as epoxidation, 1,2-dihydroxylation, and α-oxyfunctionalization of alkenes, as well as for ring contraction of cycloalkanones, conversion of halomethyl, hydroxymethyl or active methylene groups into formyl groups, oxidation of carbonyl compounds into carboxylic acids and/or lactones, sulfides into sulfoxides, and secondary amines into nitrones and regeneration of parent carbonyl compounds from their azomethine derivatives. Other reactions such as dehydrogenation and aromatization, active carbon-carbon bond cleavage, oxidative amidation, bromolactonization and oxidation of bromide for subsequent reactions with alkenes are also successfully mediated by selenium (IV) oxide or organoselenium compounds. The oxidation mechanisms of ionic or free radical character depending on the substrate and oxidant are discussed. Coverage of the literature up to early OPEN ACCESSMolecules 2015, 20 10206 2015 is provided. Links have been made to reviews that summarize earlier literature and to the methods of preparation of organoselenium reagents and catalysts.

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Dehydrogenation with benzeneseleninic anhydride in the total synthesis of ergot alkaloids

Cited by 40 publications

References 5 publications

Total Synthesis of (±)-Lysergic Acid, Lysergol, and Isolysergol by Palladium-Catalyzed Domino Cyclization of Amino Allenes Bearing a Bromoindolyl Group

Total Synthesis of (±)-Lysergic Acid, Lysergol, and Isolysergol by Palladium-Catalyzed Domino Cyclization of Amino Allenes Bearing a Bromoindolyl Group

Riley Oxidation of Heterocyclic Intermediates on Paths to Hydroporphyrins—A Review

Developments in Synthetic Application of Selenium(IV) Oxide and Organoselenium Compounds as Oxygen Donors and Oxygen-Transfer Agents

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