Application of the Swern oxidation to the manipulation of highly reactive carbonyl compounds

Ireland, Robert E.; Norbeck, Daniel W.

doi:10.1021/jo00212a041

Cited by 270 publications

(151 citation statements)

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“…The combined organic extracts were washed with brine (5 mL), dried over Na 2 SO 4 , and concentrated. The residue was purified by silica gel column chromatography (EtOAc/hexane 1:5 to 1:2, with 1.0 vol % Et 3 N) to give 7.0 mg of pyrrolidine 13 (39%) and 9.2 mg of pyrrolidine 32 (51% (28). Lithium borohydride (18.4 mg, 844¯mol) was added to a solution of 13 (30.8 mg, 84.3¯mol) and Et 2 O (1.5 mL) at room temperature.…”

Section: Tert-butylmentioning

confidence: 99%

Total Syntheses of (±)-Gephyrotoxin and (±)-Perhydrogephyrotoxin

Shirokane

Tanaka

Yoritate

et al. 2015

Bulletin of the Chemical Society of Japan

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This article describes the full details of our total syntheses of gephyrotoxin and perhydrogephyrotoxin. Our central strategy toward the total synthesis is based on the use of an N-methoxy group as a reactivity control element. The N-methoxyamide group enabled unique transformations, involving i) the direct coupling reaction of the N-methoxyamide with an aldehyde, and ii) the amide-selective reductive allylation. These reactions were never accomplished without the assistance of the N-methoxy group. The amide-selective reductive allylation of the N-methoxyamide was especially practical, and excluded a number of extra steps including protecting group manipulations and redox reactions in the total syntheses.Gephyrotoxin (1) is a constituent isolated from skin extracts of a Colombian tropical poison dart frog, Dendrobates histrionicus in 1977 (Figure 1). 1 The structure of gephyrotoxin (1) was elucidated by spectroscopic approaches, and finally determined by X-ray crystallographic analysis. Gephyrotoxin (1) consists of a tricyclic core and two distinct side chains with five stereogenic carbon centers, three of which are connected to the same nitrogen atom. It possesses an array of neurological activities including mild muscarinic activities. Kishi documented the first total synthesis of («)-gephyrotoxin (1) using a set of stereoselective hydrogenation reactions to establish all five stereocenters in 1980.2a Kishi then achieved the enantioselective total synthesis starting from L-pyroglutamic acid, which resulted in disagreement on the absolute configuration of the natural gephyrotoxin (1).2b The absolute structure of 1 remains inconclusive due to the limited supply of the natural alkaloid. In 1983, Hart reported the total synthesis of («)-gephyrotoxin (1) via cyclization of N-acyliminium ion as a key step.2c,2d Shortly after, Overman disclosed the stereoselective total synthesis of 1, whose key steps were the DielsAlder reaction of the amino diene, and stereoselective reduction using stereoelectronic effects.2e The unique structure of gephyrotoxin (1) has continuously inspired the synthetic community, resulting in a number of formal syntheses based on Kishi's route by a multitude of differing strategies. 24 Very recently, Smith reported the enantioselective total synthesis by use of an elegant cascade strategy. 2f In this full paper, we disclose full details of the development of an efficient strategy for synthesis of 1 using an N-methoxy group as a reactivity control element. 5 In particular, utilization of amide-selective nucleophilic addition enabled the concise and efficient total synthesis of 1.Our research group is engaged in a program devoted to the development of efficient strategies using unique properties of a heteroatomheteroatom bond for assembling complex natural products. Incorporation of a heteroatom to a second heteroatom dramatically changes the original reactivities, and enables new transformations, which are not realized with an isolated heteroatom. As proof of this concept, we took an interes...

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Section: Tert-butylmentioning

confidence: 99%

Total Syntheses of (±)-Gephyrotoxin and (±)-Perhydrogephyrotoxin

Shirokane

Tanaka

Yoritate

et al. 2015

Bulletin of the Chemical Society of Japan

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“…In addition, alcohols are, in general, cheaper, more commercially available, less toxic and more stable than the corresponding aldehydes. In this sense, a variety of oxidising systems have been implemented for the in situ oxi-31 dation-Wittig olefination of primary alcohols, namely, Swern, [3] MnO 2 , [4] Dess-Martin, [5] BaMnO 4 , [6] IBX, [7] TPAP, [8] PCC, [9] SO 3 ·Py [10] and BAIB [bis(acetoxy)iodobenzene]-TEMPO. [11] These procedures are primarily applied to stabilised ylides and, though in all cases the reac- 36 tions are performed in one pot, some of them are sequential.…”

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confidence: 99%

Wittig‐Type Olefination of Alcohols Promoted by Nickel Nanoparticles: Synthesis of Polymethoxylated and Polyhydroxylated Stilbenes

2009

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Nickel nanoparticles were found to promote the Wittig‐type olefination of primary alcohols with phosphorus ylides. The latter can be prepared from the corresponding phosphonium salts with nBuLi or in situ generated with lithium metal. The methodology is especially efficient for the synthesis of stilbenes and is applied in the absence of any additive as ahydrogen acceptor. A new approach to the synthesis of polymethoxylated and polyhydroxylated stilbenes, including resveratrol, DMU‐212 and analogues, is presented.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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“…21 Commercially available alcohols such as hex-5-en-1-ol were subjected to a one-pot Swern oxidation and HWE reaction to give the corresponding (E)-α,β-unsaturated esters in 69-90% yield. 22 The high yields from this one-pot two-step process arose from a combination of not having to isolate the volatile aldehyde intermediates and the mild Masamune-Roush conditions for the HWE reaction. 23 Although other organophosphorus alkene-forming reactions were investigated for the synthesis of the α,β-unsaturated esters, only the HWE reaction consistently gave the E-isomers as the sole products.…”

Section: Methodsmentioning

confidence: 99%

One-Pot Multi-Reaction Processes: Synthesis of Natural Products and Drug-Like Scaffolds

Calder

Grafton

Sutherland

2014

Synlett

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Abstract:One-pot multi-reaction processes involving Overman rearrangements, metathesis cyclizations, and Diels-Alder reactions have been developed for the rapid and efficient synthesis of aminosubstituted carbocyclic and heterocyclic compounds. This account describes the development and optimization of these processes, as well as their applications in the synthesis of natural products and drug-like scaffolds.

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Application of the Swern oxidation to the manipulation of highly reactive carbonyl compounds

Cited by 270 publications

References 1 publication

Total Syntheses of (±)-Gephyrotoxin and (±)-Perhydrogephyrotoxin

Total Syntheses of (±)-Gephyrotoxin and (±)-Perhydrogephyrotoxin

Wittig‐Type Olefination of Alcohols Promoted by Nickel Nanoparticles: Synthesis of Polymethoxylated and Polyhydroxylated Stilbenes

One-Pot Multi-Reaction Processes: Synthesis of Natural Products and Drug-Like Scaffolds

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