α, β‐Epoxyketon → Alkinon‐Fragmentierung I: Synthese von exalton und <i>rac</i> ‐ muscon aus cyclododecanon über synthetische methoden, 3. Mitteilung

Felix, Dorothée; Schreiber, J.; Ohloff, G.; Eschenmoser, Albert

doi:10.1002/hlca.19710540855

Cited by 110 publications

(29 citation statements)

References 49 publications

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“…1a). The probe 1 was synthesized efficiently through epoxidation and subsequent Eschenmoser–Tanabe fragmentation from 4-cholesten-3-one (Supplementary Scheme S1)2324.…”

Section: Resultsmentioning

confidence: 99%

“…In looking for a suitable reaction that could be used to generate the alkyne moiety, we focused on reactions that proceed well under mild conditions. We focused in particular on Eschenmoser–Tanabe fragmentation2324, where an alkyne group is converted from a stable epoxy ketone moiety by addition of TsNHNH 2 . In the previous reports, this reaction proceeded in polar solvents such as alcohols at slightly high temperatures.…”

Section: Discussionmentioning

confidence: 99%

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Chemically-activatable alkyne-tagged probe for imaging microdomains in lipid bilayer membranes

Yamaguchi

Matsushita

Izuta

et al. 2017

Sci Rep

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A chemically-activatable alkynyl steroid analogue probe has been synthesized for visualizing the lipid raft membrane domains by Raman microscopy. The Raman probe, in which ring A of its steroid backbone is replaced with an alkynyl group, was designed to enable activation of the alkyne signal through the Eschenmoser-Tanabe fragmentation reaction of the oxidized cholesterol precursor in lipid bilayer membranes. The alkynyl steroid analogue was observed to form liquid-ordered raft-like domains on a model giant-liposome system in a similar manner as cholesterol, and the large alkyne signal of the accumulated probe at 2120 cm−1 was mapped on the microdomains with a Raman microscope. The alkyne moiety of the probe was confirmed to be converted from the α,β-epoxy ketone group of its precursor by reaction with p-toluensulfonyl hydrazine under a mild condition. Through the reaction, the alkyne signal of the probe was activated on the lipid bilayer membrane of liposomes. Furthermore, the signal activation of the probe was also detected on living cells by stimulated Raman scattering microscopy. The ring-A-opened alkyne steroid analogue, thus, provides a first chemically-activatable Raman probe as a promising tool for potentially unravelling the intracellular formation and trafficking of cholesterol-rich microdomains.

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“…1a). The probe 1 was synthesized efficiently through epoxidation and subsequent Eschenmoser–Tanabe fragmentation from 4-cholesten-3-one (Supplementary Scheme S1)2324.…”

Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Chemically-activatable alkyne-tagged probe for imaging microdomains in lipid bilayer membranes

Yamaguchi

Matsushita

Izuta

et al. 2017

Sci Rep

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“…Oxidation of ketone 4 with IBX 7) followed by epoxidation afforded epoxyketone 6, which was subjected to Eschenmoser-Tanabe fragmentation. 8) However, treatment of 6 with tosyl or nosyl hydrazide recovered the starting material. Additionally, employing aminoaziridines as reagents for the same type transformation did not provide the desired product.…”

Section: Synthesis Of Mersicarpinementioning

confidence: 99%

Synthesis of Natural Products with Polycyclic Systems

Yokoshima

2013

CHEMICAL & PHARMACEUTICAL BULLETIN

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Herein we present our unique strategies to synthesize natural products. To prepare mersicarpine, an atypical indole alkaloid, our procedure features an Eschenmoser-Tanabe fragmentation to synthesize an alkyne unit, a combination of a Sonogashira coupling and a gold(III) catalyzed cyclization to construct the indole skeleton, and a one-pot process to arrange the cyclic imine and the hemiaminal moieties. Additionally, we synthesized a frog poison, histrionicotoxin, via a chirality transfer from an allenylsilane to prepare a pseudosymmetrical dienyne, dienyne metathesis to produce an optically active bicyclo [5.4.0] system, and an asymmetric propargylation. To synthesize lyconadin A, a Lycopodium alkaloid, a combination of an azaPrins reaction and electrocyclic ring opening constructed the highly fused tetracyclic compound. The synthesis of isoschizogamine features a facile construction of the carbon framework through a Wagner-Meerwein rearrangement, a tandem metathesis, a stereoselective rhodium-mediated 1,4-addition of an arylboronic acid, and a ring-closing metathesis via a hemiaminal ether.

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“…[178,179] After a Weitz-Schaefer epoxidation and the formation of a tosylhydrazone, its decomposition is carried out at 0 °C in weakly acidic media (acetic acid diluted with dichloromethane), which contrasts the otherwise similar Wolff-Kishner reduction.…”

Section: Karl Waldemar Ziegler (1898-1973)mentioning

confidence: 99%

Flavours and Fragrances

Schaefer

2014

Natural Products in the Chemical Industry

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α, β‐Epoxyketon → Alkinon‐Fragmentierung I: Synthese von exalton und rac ‐ muscon aus cyclododecanon über synthetische methoden, 3. Mitteilung

Cited by 110 publications

References 49 publications

Chemically-activatable alkyne-tagged probe for imaging microdomains in lipid bilayer membranes

Chemically-activatable alkyne-tagged probe for imaging microdomains in lipid bilayer membranes

Synthesis of Natural Products with Polycyclic Systems

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