Total Synthesis of Epicoccin G

Nicolaou, K. C.; Totokotsopoulos, Sotirios; Giguère, Denis; Sun, Ya Ping; Šarlah, David

doi:10.1021/ja2032635

Cited by 83 publications

(68 citation statements)

References 29 publications

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“…By comparison, in 2011 Nicolaou presented the total synthesis of dithiodiketopiperazines (epicoccin G and 8,8'-epi-ent-rostratin B) including two TPP-photocatalysed endoperoxide formations, and base-catalysed Kornblum DeLaMare rearrangements (Scheme 23) [90]. Singlet oxygen generation by porphyrins can take place in reactions with amines [91].…”

Section: Porphyrin Derivatives Acting As Photocatalystsmentioning

confidence: 99%

Porphyrins as Catalysts in Scalable Organic Reactions

et al. 2016

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Catalysis is a topic of continuous interest since it was discovered in chemistry centuries ago. Aiming at the advance of reactions for efficient processes, a number of approaches have been developed over the last 180 years, and more recently, porphyrins occupy an important role in this field. Porphyrins and metalloporphyrins are fascinating compounds which are involved in a number of synthetic transformations of great interest for industry and academy. The aim of this review is to cover the most recent progress in reactions catalysed by porphyrins in scalable procedures, thus presenting the state of the art in reactions of epoxidation, sulfoxidation, oxidation of alcohols to carbonyl compounds and C-H functionalization. In addition, the use of porphyrins as photocatalysts in continuous flow processes is covered.

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Section: Porphyrin Derivatives Acting As Photocatalystsmentioning

confidence: 99%

Porphyrins as Catalysts in Scalable Organic Reactions

et al. 2016

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“…Nonetheless, the structure is remarkably similar to that of epicorazine A ( 8 ), and a discussion of Nicolaou's recent total synthesis is certainly relevant in this context. 134 Hydroxy enone 243 (prepared in two steps from N -Boc-tyrosine) was converted in four steps to hydroxy methyl ester 244 (Scheme 23). Separate deprotections to either the amine or carboxylic acid gave two derivatives that were coupled to form amide 245 .…”

Section: Recent Epidithiodioxopiperazine Syntheses (2009-2013)mentioning

confidence: 99%

Epidithiodioxopiperazines. occurrence, synthesis and biogenesis

2014

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Epidithiodioxopiperazine alkaloids possess an astonishing array of molecular architecture and generally exhibit potent biological activity. Nearly twenty distinct families have been isolated and characterized since the seminal discovery of gliotoxin in 1936. Numerous biosynthetic investigations offer a glimpse at the relative ease with which Nature is able to assemble this class of molecules, while providing synthetic chemists inspiration for the development of more efficient syntheses. Herein, we discuss the isolation and characterization, proposed fungal biogeneses, and total syntheses of epidithiodioxopiperazines.

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“…In preliminary communications we already reported an improved method for the sulfenylation of 2,5-diketopiperazines 7 and the total synthesis 8 of epicoccin G 9 ( 1 , Figure 1) and 8,8′- epi - ent -rostratin B 10 ( 2 , Figure 1). In this article we describe further studies in this area that include enantioselective total syntheses of gliotoxin 11 ( 3 , Figure 1), gliotoxin G 12 ( 4 , Figure 1), emethallicin E 13 ( 5 , Figure 1) and haematocin 14 ( 6 , Figure 1), as well as the monomeric unit ( 7 , Figure 1) of aranotin 15,16 ( 8 , Figure 1).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Biological Evaluation of Epidithio-, Epitetrathio-, and bis-(Methylthio)diketopiperazines: Synthetic Methodology, Enantioselective Total Synthesis of Epicoccin G, 8,8′-epi-ent-Rostratin B, Gliotoxin, Gliotoxin G, Emethallicin E, and Haematocin and Discovery of New Antiviral and Antimalarial Agents

et al. 2012

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An improved sulfenylation method for the preparation of epidithio-, epitetrathio- and bis-(methylthio)diketopiperazines from diketopiperazines has been developed. Employing NaHMDS and related bases and elemental sulfur or bis[bis(trimethylsilyl)amino]trisulfide (23) in THF, the developed method was applied to the synthesis of a series of natural and designed molecules, including epicoccin G (1), 8,8′-epi-ent-rostratin B (2), gliotoxin (3), gliotoxin G (4), emethallicin E (5) and haematocin (6). Biological screening of selected synthesized compounds led to the discovery of a number of nanomolar anti poliovirus agents (i.e. 46, 2,2′-epi-46 and 61, Table 5) and several low micromolar anti Plasmodium falciparum lead compounds (i.e. 46, 2,2′-epi-46, 58, 61 and 1, Table 5).

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Total Synthesis of Epicoccin G

Abstract: An expedient enantioselective total synthesis of epicoccin G and related dithiodiketopiperazines through a strategy featuring direct two-directional sulfenylation, photooxygenation and Kornblum–DeLaMare rearrangement is described.

Cited by 83 publications

References 29 publications

Porphyrins as Catalysts in Scalable Organic Reactions

Porphyrins as Catalysts in Scalable Organic Reactions

Epidithiodioxopiperazines. occurrence, synthesis and biogenesis

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