Notes - Osmium Tetroxide-Catalyzed Periodate Oxidation of Olefinic Bonds

Pappo, Raphael; Allen, D. S.; Lemieux, R. U.; Johnson, WS

doi:10.1021/jo01110a606

Cited by 668 publications

(331 citation statements)

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“…Introduction of the isovaleryl group at C11 in homoallylic alcohol 14 and dihydroxylation of the terminal olefin afforded a diol, which was converted into aldehyde 15 as a C1C13 segment. This two-step procedure was superior to the direct LemieuxJohnson conditions 12 in both yield and reproducibility because of the instability of aldehyde 15.…”

Section: Resultsmentioning

confidence: 94%

Total Synthesis and Biological Evaluation of Auripyrones A and B

Hayakawa

Takemura

Fukasawa

et al. 2012

Bulletin of the Chemical Society of Japan

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The total synthesis of auripyrones was achieved by using a novel aldol-type reaction of £-pyrone as a key step. From this synthetic work, we have established the stereostructure and absolute configuration of auripyrone B. Furthermore, the cytotoxicities of auripyrones against a panel of 39 human cancer cell lines (termed JFCR39) at the Japanese Foundation for Cancer Research were investigated. The patterns of the differential cytotoxicities of auripyrones were COMPARE negative, suggesting that they inhibit cancer cell proliferation through a novel mechanism.A number of significant biologically active £-pyronecontaining compounds from marine animals have been reported.1 The structural features of these £-pyrone-containing compounds are asymmetric centers at the neighboring positions of the £-pyrone part. In 1996, Yamada and co-workers reported the isolation of auripyrones A (1) and B (2) from the sea hare Dolabella auricularia (Aplysiidae), which exhibit cytotoxicity against HeLa S 3 cells with IC 50 values of 0.26 and 0.48 g mL ¹1 , respectively ( Figure 1). 2 The relative stereochemistry of the core unit of auripyrones A (1) and B (2) was determined by an extensive analysis of coupling constants and the NOESY correlations. The main structural features of auripyrones are a £-pyrone ring and a spiroacetal moiety. The unique structures of auripyrones, in conjunction with their biological activities, have made them attractive synthetic targets. Several groups have reported approaches to the synthesis of auripyrones. In 2006, Perkins and Lister were the first to achieve the total synthesis of auripyrone A (1), featuring spiroacetalization. This synthesis established the absolute configuration of auripyrone A (1). In 2009, Jung and Salehi-Rad achieved the total synthesis of auripyrone A (1) by using a tandem non-aldol aldol/Paterson aldol process. 4 The next year, we preliminarily reported the total synthesis of auripyrones A (1) and B (2) by using a novel diastereoselective aldol-type reaction of 2,6-diethyl-3,5-dimethyl-4-pyrone (8).5 From this synthetic work, we determined the absolute configuration of auripyrone B (2). Very recently, Jung and co-workers reported the total synthesis of auripyrone B (2) using their previous strategy. 6 We describe herein the detailed synthesis of auripyrones A (1) and B (2) and their cytotoxicities against a panel of 39 human cancer cell lines. Results and DiscussionOur retrosynthetic analyses of auripyrones A (1) and B (2) are shown in Scheme 1. Auripyrones A (1) and B (2) can be obtained from triketone 3 by using spiroacetalization. Triketone 3 can be derived from C1C13 segment 4 and C14C20 segment 5 by using the aldol coupling reaction. Asymmetric centers at C11 and C12 of C1C13 segment 4 can be constructed from aldehyde 7 by asymmetric crotylboration. Aldehyde 7, which possesses an asymmetric center at the neighboring position of £-pyrone, can be synthesized from 2,6-diethyl-3,5-dimethyl-4-pyrone (8) and the optically active aldehyde 9 by diastereoselective aldol-type reaction ...

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Section: Resultsmentioning

confidence: 94%

Total Synthesis and Biological Evaluation of Auripyrones A and B

Hayakawa

Takemura

Fukasawa

et al. 2012

Bulletin of the Chemical Society of Japan

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“…Our approach to the synthesis of fluoxetine hydrochloride [(R)-1.HCl] centered on the treatment of benzaldehyde (2) 2 Cl 2 )} was carried out by oxidative cleavage according to the Lemieux-Johnson protocol, 43 followed by NaBH 4 reduction of the crude aldehyde (87% overall yield). The secondary amino functionality was introduced next via the corresponding mesylate 5 which was regioselectively prepared in 85% yield via treatment of diol 4 with mesyl chloride (1.0 equiv.)…”

Section: Resultsmentioning

confidence: 99%

A concise total synthesis of (R)-fluoxetine, a potent and selective serotonin reuptake inhibitor

Fátima¹,

Lapis²,

Pilli³

2005

J. Braz. Chem. Soc.

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(R)-Fluoxetina, um inibidor potente e seletivo da recaptação da serotonina, foi sintetizada em seis etapas, 50% de rendimento total e 99% de excesso enantiomérico a partir do benzaldeído via alilação catalítica assimétrica empregando-se o sistema catalítico desenvolvido por Maruoka e colaboradores.(R)-Fluoxetine, potent and selective serotonin reuptake inhibitor, has been synthesized in six steps, 50% overall yield and 99% ee from benzaldehyde via catalytic asymmetric allylation with Maruoka´s catalyst.

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“…Benzyloxyacetaldehyde (5) was obtained in 78% overall yield from benzyl alcohol by treatment with sodium hydride and allyl bromide, followed by oxidative cleavage according to the Lemieux-Johnson protocol 11 . In the event, reaction of benzyloxyacetaldehyde (5) 19 in CH 2 Cl 2 at rt achieved debenzylation of 8 to give 9 in 88% yield.…”

Section: Resultsmentioning

confidence: 99%