Phosphine-Mediated Coupling of Gramines with Aldehydes:  A Remarkably Simple Synthesis of 3-Vinylindoles

Low, Kam‐Hung; Magomedov, Nabi A.

doi:10.1021/ol050484+

Cited by 36 publications

(15 citation statements)

References 38 publications

(21 reference statements)

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“…In 2005, Magomedov and co-workers disclosed a method to access phosphorus ylides by treating gramine with tributylphosphine (Scheme 710). 798 Through the assistance of the phosphine, elimination of dimethylamine occurs to give the enimine 450 . After proton transfers, the ylide 451 is obtained.…”

Section: Ylides Formed Through Nucleophilic Addition Of Phosphinementioning

confidence: 99%

Phosphine Organocatalysis

et al. 2018

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The hallmark of nucleophilic phosphine catalysis is the initial nucleophilic addition of a phosphine to an electrophilic starting material, producing a reactive zwitterionic intermediate, generally under mild conditions. In this Review, we classify nucleophilic phosphine catalysis reactions in terms of their electrophilic components. In the majority of cases, these electrophiles possess carbon–carbon multiple bonds: alkenes (section 2), allenes (section 3), alkynes (section 4), and Morita–Baylis–Hillman (MBH) alcohol derivatives (MBHADs; section 5). Within each of these sections, the reactions are compiled based on the nature of the second starting material—nucleophiles, dinucleophiles, electrophiles, and electrophile–nucleophiles. Nucleophilic phosphine catalysis reactions that occur via the initial addition to starting materials that do not possess carbon–carbon multiple bonds are collated in section 6. Although not catalytic in the phosphine, the formation of ylides through the nucleophilic addition of phosphines to carbon–carbon multiple bond–containing compounds is intimately related to the catalysis and is discussed in section 7. Finally, section 8 compiles miscellaneous topics, including annulations of the Hüisgen zwitterion, phosphine-mediated reductions, iminophosphorane organocatalysis, and catalytic variants of classical phosphine oxide–generating reactions.

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Section: Ylides Formed Through Nucleophilic Addition Of Phosphinementioning

confidence: 99%

Phosphine Organocatalysis

et al. 2018

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“…A facile PBu 3 -mediated olefination between gramines 54 and aldehydes was developed by Magomedov and co-workers 32 for the construction of synthetically versatile 3-vinylindoles 55 with excellent E-selectivity (Scheme 19). Aromatic aldehydes provided good to excellent yields while aliphatic aldehydes gave low yields, presumably due to the diminished stability of the alkyl-substituted vinylindole products.…”

Section: Reactions Based On Other Substratesmentioning

confidence: 99%

Recent advances in stoichiometric phosphine-mediated organic synthetic reactions

2013

RSC Adv.

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Silong Xu a and Zhengjie He* b Organic synthetic reactions mediated by tertiary phosphines have attracted much attention in the organic chemistry community in the past two decades. These reactions can be divided into two categories: phosphine-catalyzed and stoichiometric phosphine-mediated transformations. While the phosphinecatalyzed reactions mechanistically rely on the unique properties of tertiary phosphines such as excellent nucleophilicity and good leaving group ability, the stoichiometric transformations are usually driven by nucleophilicity and strong oxyphilicity of tertiary phosphines. Since tertiary phosphines represent an important class of versatile chemical reagents in organic synthesis, stoichiometric phosphine-mediated reactions have recently demonstrated their uniqueness and high efficiency in organic synthesis, particularly with respect to the construction of carbon-carbon and carbon-heteroatom bonds, and therefore have stimulated much research interest. In this review, recent advances in stoichiometric phosphine-mediated reactions primarily including olefinations and annulations are summarized.

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“…1 F16. F16 was synthesized according to the literature (14), and some procedures were modified. Briefly, 0.20 mL of pyridinecarboxaldehyde (2.00 mmol) and 0.74 mL of N-butyl phosphorus (3.00 mmol) were added to a solution of 348 mg (2.00 mmol) of gramine in 5.0 mL of dry acetonitrile at room temperature.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of F16 conjugated with 5‐fluorouracil and biophysical investigation of its interaction with bovine serum albumin by a spectroscopic and molecular modeling approach

Chen

et al. 2012

Luminescence

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5-Fluorouracil (5-FU) has been widely used as a chemotherapy agent in the treatment of many types of solid tumors. Investigation of its antimetabolites led to the development of an entire class of fluorinated pyrimidines. However, the toxicity profile associated with 5-FU is significant and includes diarrhea, mucositis, hand-foot syndrome and myelosuppression. In aiming at reducing of the side effects of 5-FU, we have designed and synthesized delocalized lipophilic cations (DLCs) as a vehicle for the delivery of 5-FU. DLCs accumulate selectively in the mitochondria of cancer cells because of the high mitochondrial transmembrane potential (ΔΨm). Many DLCs exhibited anti-cancer efficacy and were explored as potential anti-cancer drugs based on their selective accumulation in the mitochondria of cancer cells. F16, the DLC we used as a vehicle, is a small molecule that selectively inhibits tumor cell growth and dissipates mitochondrial membrane potential. The binding of the conjugate F16-5-FU to bovine serum albumin (BSA) was investigated using spectroscopic and molecular modeling approaches. Fluorescence quenching constants were determined using the Stern-Volmer equation to provide a measure of the binding affinity between F16-5-FU and BSA. The activation energy of the interaction between F16-5-FU and BSA was calculated and the unusually high value was discussed in terms of the special structural block indicated by the molecular modeling approach. Molecular modeling showed that F16-5-FU binds to human serum albumin in site II, which is consistent with the results of site-competitive replacement experiments. It is suggested that hydrophobic and polar forces played important roles in the binding reaction, in accordance with the results of thermodynamic experiments.

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Phosphine-Mediated Coupling of Gramines with Aldehydes: A Remarkably Simple Synthesis of 3-Vinylindoles

Abstract: A new and practical synthesis of terminally substituted 3-vinylindoles is described involving tributylphosphine-mediated coupling of gramines with aldehydes.

Cited by 36 publications

References 38 publications

Phosphine Organocatalysis

Phosphine Organocatalysis

Recent advances in stoichiometric phosphine-mediated organic synthetic reactions

Synthesis of F16 conjugated with 5‐fluorouracil and biophysical investigation of its interaction with bovine serum albumin by a spectroscopic and molecular modeling approach

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