Oxidation of alcohols by “activated” dimethyl sulfoxide. a preparative, steric and mechanistic study

Omura, Kanji; Swern, Daniel

doi:10.1016/0040-4020(78)80197-5

Cited by 1,216 publications

(557 citation statements)

References 14 publications

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“…Over the past 20 years, numerous studies have established a general scheme for the biosynthetic pathway of a major class of Lepidopteran sex pheromone components in which the common C 16 or C 18 FA intermediate is stepwise converted to the final components through various combinations of chain-shortening and desaturation reactions that are then followed by reductive modifications of the carbonyl carbon (3). For the biosynthesis of such pheromone components, various pheromone gland-specific desaturases with diverse regio-and stereospecificities have been shown to contribute significantly to the generation of speciesspecific pheromone components (4).…”

Section: Discussionmentioning

confidence: 99%

“…E10,E12-16:Me and E10,Z12-16:Me were prepared from their corresponding acids (7). E12,Z14-18:Me and E12,E14-18:Me were synthesized from 12-[(tert-butyldimethylsilyl)oxy]-1-dodecanol (15), which was oxidized under Swern's conditions (16) and then subjected to the Wittig-Horner-Emmons reaction (17). Diisobutylaluminum hydride reduction of the resulting product, ethyl (E)-14-[(tertbutyldimethylsilyl)oxy]-2-tetradecenoate, followed by MnO 2 oxidation yielded the corresponding aldehyde, which was converted to E12,Z14-18:acid by the same method as used for the preparation of E10,Z12-16:acid (7).…”

Section: Construction Of Recombinant Baculovirusesmentioning

confidence: 99%

“…A major class of sex pheromone components produced by these female moths has been characterized by the presence of straightchain C 10 -C 18 unsaturated aliphatic compounds containing an oxygenated functional group (aldehyde, alcohol, or acetate ester) derived from saturated C 16 or C 18 fatty acid (FA) intermediates that are synthesized de novo in the abdominal pheromone gland cells (2).…”

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confidence: 99%

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Involvement of a bifunctional fatty-acyl desaturase in the biosynthesis of the silkmoth, Bombyx mori , sex pheromone

Moto

Suzuki

Hull

et al. 2004

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

114

116

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The straight-chain C10 to C18 unsaturated aliphatic compounds containing an oxygenated functional group (aldehyde, alcohol, or acetate ester) derived from saturated C 16 or C18 fatty acids are a major class of sex pheromone components produced by female moths. In the biosynthesis of these pheromone components, various combinations of limited chain-shortening and regio-and stereospecific desaturation reactions significantly contribute to the production of a vast number of the species-specific pheromone components in Lepidoptera. Biosynthesis of the silkmoth sex pheromone bombykol, (E,Z)-10,12-hexadecadien-1-ol, involves two consecutive desaturation steps, the second of which is unique in that it generates a conjugated diene system from the ⌬11-monoene C 16 intermediate. In experiments designed to characterize the acyl-CoA desaturases responsible for bombykol biosynthesis, we have cloned three cDNAs encoding desaturase family members from the pheromone gland of the inbred strain of the silkmoth, Bombyx mori. Transcript analyses by RT-PCR and subsequent functional assays using a Bac-to-Bac baculovirus expression system revealed that desat1 is the only desaturase gene prominently expressed during pheromonogenesis and that its gene product, B. mori Desat1, possesses both Z11 desaturation and ⌬10,12-desaturation activities. Consequently, we have concluded that B. mori Desat1 is not only a bifunctional desaturase involved in bombykol biosynthesis but that it is also the enzyme responsible for both desaturation steps.

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Section: Discussionmentioning

confidence: 99%

Section: Construction Of Recombinant Baculovirusesmentioning

confidence: 99%

mentioning

confidence: 99%

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Involvement of a bifunctional fatty-acyl desaturase in the biosynthesis of the silkmoth, Bombyx mori , sex pheromone

Moto

Suzuki

Hull

et al. 2004

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

114

116

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“…Next, the piperidine nitrogen was protected by treatment with benzylbromide 33,34 and the hydroxyl group was subsequently transformed into the corresponding aldehyde via a Swern oxidation. 35 The aldehyde group was readily converted to an imidazole ring using TosMIC chemistry. 36 Some of the intermediate 4-tosyloxazolines (27a-c) precipitated from the solution and were used after filtration.…”

Section: Chemistrymentioning

confidence: 99%

Synthesis and Structure−Activity Relationships of Conformationally Constrained Histamine H₃ Receptor Agonists

et al. 2003

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Immepip, a conformationally constrained analogue of the histamine congener imbutamine, shows high affinity and functional activity on the human H 3 receptor. Using histamine and its homologues as prototypes, other rigid analogues containing either a piperidine or pyrrolidine ring in the side chain were synthesized and tested for their activities at the human H 3 receptor and the closely related H 4 receptor. In the series of piperidine containing analogues, immepip was found to be the most potent H 3 receptor agonist, whereas its propylene analogue 13a was identified as a high-affinity neutral antagonist for the human H 3 receptor. Moreover, replacement of the piperidine ring of immepip by a pyrrolidine ring led to a pair of enantiomers that show a distinct stereoselectivity at the human H 3 and H 4 receptor.

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“…The magnitude of diastereoselectivity of the alkylation was determined to be >10:1 after reductive removal of the auxiliary using lithium amidotrihydroborate (LAB). 12 The resulting primary alcohol 17 was then oxidized to the corresponding aldehyde under Swern conditions 13 , which was subjected to Takai iodoolefination to give the (E)-vinyl iodide 8 (E/Z > 20:1, 75% yield). 14 The short sequence required for the elaboration of the cis-2,6-trans-5,6-tetrahydropyran core is summarized in Scheme 3.…”

Section: Nih Public Access Author Manuscriptmentioning

confidence: 99%

Total Synthesis of Herboxidiene/GEX 1A.

Zhang

Panek

2007

ChemInform

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A convergent enantioselective synthesis of herboxidiene/GEX 1A (1) is described, which features a double stereodifferentiating crotylation, [4+2]-annulation and a silicon-based sp 2 -sp 2 crosscoupling to assemble the conjugated diene.Herboxidiene/GEX 1A (1), a secondary metabolite originally isolated from Streptomyces sp. A7847, displayed selective phytotoxicity against a range of broadleaf annual weeds while remaining harmless to coplanted wheat. 1 In a search for new antitumor agents, 1 was reisolated from a fermentation culture broth with five other structurally related GEX 1 members (2-6, Figure 1). 2 While several members of this family showed potent cytotoxicity (IC 50 values ranging from 3.7 nM to 0.99 μM) against several human tumor cell lines in vitro, GEX 1A is the only one possessing antitumor activity in vivo. The entire family of GEX 1 compounds displayed cytotoxicity via up-regulating luciferase reporter gene expression as well as inducing both G1 and G2/M arrest in human tumor cell line The stereochemical assignment of 1 was obtained through a combination of degradation studies, partial synthesis and crystallographic analysis. 4 The class of natural products possesses several synthetically challenging structural features, including the trisubstituted tetrahydropyran core, the conjugated diene moiety and the poly-oxygenated side chain. Two total syntheses and several synthetic approaches toward herboxidiene/GEX 1A have recently been published. 5 Herein, we describe a convergent enantioselective total synthesis of herboxidiene/GEX 1A (1) that makes use of organosilane based bond construction methodology in three crucial ways (Scheme 1). The first disconnection at C9-C10 leads to a functionalized pyran core and an oxygenated side chain. We anticipated using a silicon-assisted sp 2 -sp 2 cross-coupling for panek@bu.edu. Supporting Information Available Experimental details and new selected spectral for all new compounds. This material is available free of charge in the Internet at http://pubs.acs.org. the union of intermediates 7 and 8. In this plan, the conjugated (E, E)-diene could be accessed with high levels of selectivity. Dihydropyran 7 could be obtained from syn-silane reagent 9 and the silyl-substituted methacrolein 10 utilizing our stereoselective [4+2]-annulation strategy. 6 Further, we hoped that side chain 11 could be rapidly constructed from silane reagent (S)-12 and α-silyloxy acetal (S)-13. NIH Public AccessSynthesis of the C10-C19 fragment was initiated with a double stereodifferentiating crotylation 7 based on the use of a newly developed crotylsilane reagent (S)-12 that bears a fully substituted stereocenter (Scheme 2). 8 Since the C18 hydroxyl would be properly configured for a directed epoxidation later in the synthesis, we chose (S)-silyloxy acetal 13, as the crotylation electrophile. 9 Thus, a matched crotylation between (S)-12 and (S)-13 promoted by TMSOTf, provided the desired syn-homoallylic ether 11 containing a trans trisubstituted olefin in 62% yield and high dias...

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Oxidation of alcohols by “activated” dimethyl sulfoxide. a preparative, steric and mechanistic study

Cited by 1,216 publications

References 14 publications

Involvement of a bifunctional fatty-acyl desaturase in the biosynthesis of the silkmoth, Bombyx mori , sex pheromone

Involvement of a bifunctional fatty-acyl desaturase in the biosynthesis of the silkmoth, Bombyx mori , sex pheromone

Synthesis and Structure−Activity Relationships of Conformationally Constrained Histamine H₃ Receptor Agonists

Total Synthesis of Herboxidiene/GEX 1A.

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Oxidation of alcohols by “activated” dimethyl sulfoxide. a preparative, steric and mechanistic study

Cited by 1,216 publications

References 14 publications

Involvement of a bifunctional fatty-acyl desaturase in the biosynthesis of the silkmoth, Bombyx mori , sex pheromone

Involvement of a bifunctional fatty-acyl desaturase in the biosynthesis of the silkmoth, Bombyx mori , sex pheromone

Synthesis and Structure−Activity Relationships of Conformationally Constrained Histamine H3 Receptor Agonists

Total Synthesis of Herboxidiene/GEX 1A.

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Synthesis and Structure−Activity Relationships of Conformationally Constrained Histamine H₃ Receptor Agonists