Conformation and Cope rearrangement of sym-oxepin oxides

Rastetter, William H.; Richard, Thomas J.

doi:10.1021/ja00508a029

Cited by 15 publications

(4 citation statements)

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“…35 Thus, bicyclic diene system 90 (for its synthesis see Scheme 9, 77 → 78 , step h) was reacted with bis -trichloroethylazodicarboxylate (TrocN=NTroc) to afford Diels–Alder adduct 91 stereoselectively (steric control) and in 93% yield. Desilylation of the latter with TBAF gave hydroxy derivative 92 (92% yield), whose treatment with methyl(trifluoromethyl) dioxirane followed by sequential exposure to Zn and CuCl 2 in the presence of NH 4 OH afforded diazo epoxide 93 as a single diastereoisomer (76% overall yield).…”

Section: Resultsmentioning

confidence: 99%

“…As expected, this epoxide did not enter the obligatory rearrangement with loss of N 2 by virtue of the syn arrangement of the diazo and epoxide moieties that does not allow for the proper orbital orientations. 35a …”

Section: Resultsmentioning

confidence: 99%

“…As part of a program directed toward the total synthesis of aranotin ( 8 ) we attempted to construct its monomeric unit ( 7 , see Scheme ) through diazo epoxide precursor 95 as shown in Scheme . Thus, bicyclic diene system 90 (for its synthesis see Scheme , 77 → 78 , step h) was reacted with bis-trichloroethylazodicarboxylate (TrocNNTroc) to afford Diels–Alder adduct 91 stereoselectively (steric control) and in 93% yield.…”

Section: Resultsmentioning

confidence: 99%

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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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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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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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“…The additional shift of up to about 40 ppm has contributions characteristic of olefinic bridgehead carbon atoms [11] and the effect of the oxo bridge. [12] While 3 has two signals in the range of aliphatic bridgehead carbon atoms (C-1/5, 65-75 ppm), 4a and 4b each have only one (C-5, slightly more shifted). Instead, 4a and 4b each show an additional signal in the methylene carbon atom range (C-3, 21.3 and 16.4 ppm) with Sn,C couplings (Ͼ360 Hz) showing that the Me 3 Sn group is located at C-3.…”

Section: Deprotonation and Stannylationmentioning

confidence: 99%

Metalation of 9‐Oxabicyclo[3.3.1]nonadiene – the Deprotonation Path to Bridgehead Olefins

Bassioni

Köhler

2006

Eur J Org Chem

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A new route to bridgehead olefins based on a deprotonation reaction has been established. The deprotonation of 9-oxabicyclo[3.3.1]nonadiene (1) with tBuLi/TMEDA occurs selectively in the allylic position. Whilst 1 has four allyl positions, only one bridgehead proton was removed, as demonstrated by quenching with Me 3 SnCl, Me 3 SiOTf, and Me 3 PbCl. With a threefold excess of deprotonating agent and subsequent treatment with Me 3 SnCl, three stannylated derivatives -3, 4a, and 4b -were obtained. Compound 3 is the starting diene 1 substituted at the bridgehead position 1 in the skeleton, and when smaller quantities of deprotonating agent were used it was the only stannylated derivative of 1 formed. Compounds 4a and 4b had each undergone a shift of one double bond to give bridgehead olefins exo-and endo-stannylated at position 3 in the skeleton. The common intermediate pre-

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Structure-activity relationships in the mutagenicity and cytotoxicity of putative metabolites and related analogs of benzene derived from the valence tautomers benzene oxide and oxepin

Stark

Rastetter²

1996

Environ. Mol. Mutagen.

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Conformation and Cope rearrangement of sym-oxepin oxides

Cited by 15 publications

References 5 publications

Metalation of 9‐Oxabicyclo[3.3.1]nonadiene – the Deprotonation Path to Bridgehead Olefins

Structure-activity relationships in the mutagenicity and cytotoxicity of putative metabolites and related analogs of benzene derived from the valence tautomers benzene oxide and oxepin

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