Reactivity-selectivity in the Swern oxidation of alcohols using dimethyl sulfoxide-oxalyl chloride

Marx, Michael; Tidwell, Thomas T.

doi:10.1021/jo00179a009

Cited by 70 publications

(41 citation statements)

References 2 publications

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“…Semi-hydrogenation of the C≡C triple bond of 4 over Lindlar catalyst (5% of Pd on BaSO 4 ) in hexane formed 5 favorably in 2 h via 1 H NMR spectrum detection (Scheme 4). However, common Swern oxidation [21] of 5 failed to afford (Z)-undec-2-enal 6 but formed its isomer (E)-undec-2-enal 6′. Previous reports indicated that (Z)-enals could readily undergo isomerization to afford (E)-enals [22,23].…”

Section: Scheme 1 Structures Of Two Insect Pheromonesmentioning

confidence: 98%

Asymmetric synthesis of Anomala Osakana Pheromone isomer using protecting group free strategy

Lin

Zhao

et al. 2010

Chin. Sci. Bull.

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The protecting group free synthesis of Anomala Osakana Pheromone isomer has been achieved with high enantioselectivity (92% ee). A chiral γ-hydroxy-α, β-acetylenic ester was used as the key intermediate, which was obtained via asymmetric alkynylation of aldehyde. This was followed by readily handled selective hydrogenation and lactonization in three steps with a high overall yield (86%). total synthesis, swern oxidation, asymmetric alkynylation, chiral γ-butyrolactone, γ-hydroxy-α, β-acetylenic ester Citation: Lin L, Li A N, Zhao Q Y, et al. Asymmetric synthesis of Anomala Osakana Pheromone isomer using protecting group free strategy. Chiral γ-butyrolactone frameworks are present in plenty of natural products [1,2] such as flavor components [3], sex pheromones [4] of different insects and plant-growth regulators [5,6]. They are also represented as important synthetic intermediates for many bioactive compounds [7−9], which makes them significant lead structures for new drug discoveries. It is noteworthy that only one enantiomer of these chiral compounds displays strong bioactivity in general [10]. A few enantioselective synthetic approaches to the chiral γ-butyrolactones have been reported [11−14].We have expanded the synthetic application of the asymmetric alkynylation to high enantioselective synthesis of two insect pheromones, Anomala Osakana Pheromone and Janus Integer Pheromone [15] (Scheme 1). The synthesis involved exploring chiral γ-hydroxy-α, β-acetylenic esters as key intermediates 10 (Scheme 2), which were obtained via asymmetric addition of methyl propiolate (MPA) to aldehydes 11 with 84% ee. Therefore, the enantioselectivity needs to be improved.In our previous studies, lower enantioselectivity was obtained in the asymmetric addition of MPA to aliphatic al-*Corresponding author ( Scheme 1 Structures of two insect pheromones.Scheme 2 Key synthetic step analysis. dehyde than that to aromatic aldehyde as well as α, β-unsaturated aldehyde [16]. This may be caused by the rapid background reaction while using aliphatic aldehyde as the substrate. Because aliphatic aldehyde is more reactive than either aromatic or α,β-unsaturated aldehyde in the nucleophilic addition [17,18], we suggested to explore α, β-unsaturated aldehyde 6 (Scheme 3) as the substrate in the asymmetric alkynylation to improve the enantioselectivity in the synthesis of the key intermediate, chiral γ-hydroxy-α,β-acetylenic ester 7.

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Section: Scheme 1 Structures Of Two Insect Pheromonesmentioning

confidence: 98%

Asymmetric synthesis of Anomala Osakana Pheromone isomer using protecting group free strategy

Lin

Zhao

et al. 2010

Chin. Sci. Bull.

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“…After stirring for a further 15 min at À78 C, N,N-diisopropylethylamine (2.83 mL, 2.10 g, 16.3 mmol) was added, and the reaction mixture was allowed to warm to room temperature. Reactivity-selectivity relationships in the Swern oxidation of alcohols using dimethyl sulfoxide/oxalyl chloride have been investigated [1378]. sodium hydrogen carbonate solution (10 mL).…”

Section: Swern Oxidationmentioning

confidence: 99%

Phosgenation Reactions: Sections 4.5.3–4.8

2003

Phosgenations ‐ a Handbook

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“…The uronic acid was formed only to a minor extent as shown by TLC. It may be mentioned that the Swern oxidation [33] and the use of 4-acetylamino-TEMPO [34] gave less satisfying results [16]. The aldehyde then was oxidized with sodium chlorite [3.5] to furnish the uronic acid which was immediately converted into the uronamide using Staab's method [36].…”

Section: Retrosynthetic Disconnection Of the Moenomycintype Lipid I1 mentioning

confidence: 99%

A Moenomycin-type Structural Analogue of Lipid II some possible mechanisms of the mode of action of transglycosylase inhibitors can be discarded

et al. 1997

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The transglycosylation step in the peptidoglycan biosynthesis belongs to the general class of glycosyltransferase‐catalyzed reactions. The structural analogue 2 of moenomycin A has been synthesized and has been found to be antibiotically inactive. The assumption that moenomycin‐type transglycosylase inhibitors such as 1 bind at the donor site of the enzyme and that their mode of action is the result of the high stability of the sugar → phosphate bond seems to be ruled out by the present results.

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Reactivity-selectivity in the Swern oxidation of alcohols using dimethyl sulfoxide-oxalyl chloride

Cited by 70 publications

References 2 publications

Asymmetric synthesis of Anomala Osakana Pheromone isomer using protecting group free strategy

Asymmetric synthesis of Anomala Osakana Pheromone isomer using protecting group free strategy

Phosgenation Reactions: Sections 4.5.3–4.8

A Moenomycin-type Structural Analogue of Lipid II some possible mechanisms of the mode of action of transglycosylase inhibitors can be discarded

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