Oxidation of Primary Alcohols to Carboxylic Acids with Sodium Chlorite Catalyzed by TEMPO and Bleach

Zhao, Mangzhu; Li, Jing; Mano, Eiichi; Song, Zhiguo J.; Tschaen, David M.; Grabowski, Edward J. J.; Reider, Paul J.

doi:10.1021/jo982143y

Cited by 455 publications

(304 citation statements)

References 13 publications

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“…Using the hindered borane 9-borabicyclo[3.3.1]nonane (9-BBN) a 79.3% yield of alcohol compound 2 was achieved as an 85∶15 mixture (by 1 H − NMR) of epimers with the desired R-epimer predominating. Several methods reported to convert primary alcohols to carboxylic acids in one step (24,25) produced complex mixtures from compound 2, presumably due to interaction with the olefinic linkage at the 4-position. Thus a two-step oxidation sequence was employed in which SO 3 pyridine complex (26) oxidized compound 2 to aldehyde compound 3 (76.4%) followed by treatment of compound 3 with the oxidant NaOCl 2 in DMSO (27,28) to form compound 4 (79.9%).…”

Section: Resultsmentioning

confidence: 99%

Production of amorphadiene in yeast, and its conversion to dihydroartemisinic acid, precursor to the antimalarial agent artemisinin

Westfall

Pitera

Lenihan

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

633

448

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Malaria, caused by Plasmodium sp , results in almost one million deaths and over 200 million new infections annually. The World Health Organization has recommended that artemisinin-based combination therapies be used for treatment of malaria. Artemisinin is a sesquiterpene lactone isolated from the plant Artemisia annua . However, the supply and price of artemisinin fluctuate greatly, and an alternative production method would be valuable to increase availability. We describe progress toward the goal of developing a supply of semisynthetic artemisinin based on production of the artemisinin precursor amorpha-4,11-diene by fermentation from engineered Saccharomyces cerevisiae , and its chemical conversion to dihydroartemisinic acid, which can be subsequently converted to artemisinin. Previous efforts to produce artemisinin precursors used S. cerevisiae S288C overexpressing selected genes of the mevalonate pathway [Ro et al. (2006) Nature 440:940–943]. We have now overexpressed every enzyme of the mevalonate pathway to ERG20 in S. cerevisiae CEN.PK2, and compared production to CEN.PK2 engineered identically to the previously engineered S288C strain. Overexpressing every enzyme of the mevalonate pathway doubled artemisinic acid production, however, amorpha-4,11-diene production was 10-fold higher than artemisinic acid. We therefore focused on amorpha-4,11-diene production. Development of fermentation processes for the reengineered CEN.PK2 amorpha-4,11-diene strain led to production of > 40 g/L product. A chemical process was developed to convert amorpha-4,11-diene to dihydroartemisinic acid, which could subsequently be converted to artemisinin. The strains and procedures described represent a complete process for production of semisynthetic artemisinin.

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Section: Resultsmentioning

confidence: 99%

Production of amorphadiene in yeast, and its conversion to dihydroartemisinic acid, precursor to the antimalarial agent artemisinin

Westfall

Pitera

Lenihan

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

633

448

View full text Add to dashboard Cite

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“…A one-step procedure that involved the used of a combination of TEMPO, NaOCl, and NaClO 2 together was not successful, probably due to the instability of NaClO 2 /NaOCl mixture. [19] The excellent yields and extraordinary functional group compatibility achieved by using our oxidation procedure are related with the relatively high loading of TEMPO employed (0.3 equiv per hydroxyl group), as slower reaction was observed with less TEMPO. Furthermore, the two-phase condition (methylene chloride and water) for the TEMPO/NaOCl oxidation is crucial.…”

Section: Resultsmentioning

confidence: 92%

“…Despite prolonged reaction time and repeated trials, the reaction of 1 with TEMPO/NaOCl [14][15][16] led to multiple partially oxidized products with a trace amount of the desired tricarboxylic acid 2. Attempts with TEMPO/BAIB [18] or NaClO 2 catalyzed by NaOCl/ TEMPO [19] met with similar fate. A two-step process of Dess-Martin oxidation followed by NaClO 2 [20] gave inconsistent results.…”

Section: Resultsmentioning

confidence: 99%

A Facile Method for Oxidation of Primary Alcohols to Carboxylic Acids and Its Application in Glycosaminoglycan Syntheses

Huang

Teumelsan

Huang

2006

Chemistry A European J

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A convenient two-step, one-pot procedure was developed for the conversion of primary alcohols to carboxylic acids. The alcohol was first treated with NaOCl and TEMPO under phase-transfer conditions, followed by NaClO 2 oxidation in one pot. This reaction is applicable to a wide range of alcohols and the mild reaction conditions are compatible with many sensitive functional groups, including electron-rich aromatic rings, acid-labile isopropylidene ketal and glycosidic linkages, and oxidation-prone thioacetal, p-methoxybenzyl, and allyl moieties. Several glycosaminoglycans such as heparin, chondroitin, and hyaluronic acid oligosaccharides have been synthesized in high yields by using this new oxidation protocol.

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“…Other direct oxidation methods of the primary alcohol to the carboxylic acid were considered, including the 2,2,6,6-tetramethyl-1-piperidinyloxy (free radical)͞NaClO 2 ͞NaOCl combination; unfortunately, no desired carboxylic acid product was observed (38). Finally, after exhaustive experimentation [Swern oxidation (39), SO 3 ⅐pyridine, Dess-Martin periodinane (40), o-iodoxybenzoic acid (41,42), and other 2,2,6,6-tetramethyl-1-piperidinyloxy systems (43)], it was found that a two-step protocol proved successful in obtaining the desired carboxylic acid.…”

Section: Resultsmentioning

confidence: 99%

A concise, total synthesis of the TMC-95A/B proteasome inhibitors

Albrecht

Williams

2004

Proc. Natl. Acad. Sci. U.S.A.

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A concise, total synthesis of the proteasome inhibitors TMC-95A͞B has been accomplished. The synthesis features the use of an L-serine-derived E-selective modified Julia olefination reaction to ultimately control the stereochemical outcome of the highly oxidized tryptophan fragment. Additionally, the limited use of protecting groups at a late stage of the total synthesis allowed for its completion in an efficient manner.Julia olefination ͉ Suzuki biaryl coupling ͉ Stille coupling

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Oxidation of Primary Alcohols to Carboxylic Acids with Sodium Chlorite Catalyzed by TEMPO and Bleach

Cited by 455 publications

References 13 publications

Production of amorphadiene in yeast, and its conversion to dihydroartemisinic acid, precursor to the antimalarial agent artemisinin

Production of amorphadiene in yeast, and its conversion to dihydroartemisinic acid, precursor to the antimalarial agent artemisinin

A Facile Method for Oxidation of Primary Alcohols to Carboxylic Acids and Its Application in Glycosaminoglycan Syntheses

A concise, total synthesis of the TMC-95A/B proteasome inhibitors

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