A New Protocol for Total Synthesis of Natural Product Frutinone A and Its Derivatives

2016 ◽  
Vol 69 (1) ◽  
pp. 98 ◽  
Author(s):  
Kang Lei ◽  
Dong-Wei Sun ◽  
Yuan-Yuan Tao ◽  
Xiao-Hua Xu
Keyword(s):  
Total Synthesis ◽  
Natural Product ◽  
Good Yield ◽  
Substitution Reaction ◽  
High Tolerance ◽  
Synthetic Route ◽  
Reaction Conditions ◽  
One Pot ◽  
Metal Free ◽  
Intramolecular Nucleophilic Substitution

A new protocol for total synthesis of natural product frutinone A was accomplished in three steps by using inexpensive 2′-hydroxyacetophenone as starting material. The key intermediate 3-(2-chlorobenzoyl)-4-hydroxycoumarin was synthesized in one pot through Baker–Venkataraman rearrangement of 2-acetylphenyl 2-chlorobenzoate followed by introduction of methyl chloroformate under basic conditions. Then, base-promoted intramolecular nucleophilic substitution reaction of 3-(2-chlorobenzoyl)-4-hydroxycoumarin provided frutinone A in excellent yield. The synthetic route features good yield, transition metal-free and mild reaction conditions, and high tolerance for functionality, thereby allowing easy substitutions around the frutinone A core.

Synthesis of benzofuro[2,3-c]pyridines via a one-pot three-component reaction

2014 ◽  
Vol 12 (27) ◽  
pp. 4885-4889 ◽  
Author(s):  
Jiaxing Hu ◽  
Zhihong Deng ◽  
Xueqiong Zhang ◽  
Fanglin Zhang ◽  
Hua Zheng
Keyword(s):  
Synthetic Route ◽  
Reaction Conditions ◽  
One Pot ◽  
Metal Free ◽  
One Pot Synthesis ◽  
Three Component Reaction

A convenient one-pot synthesis of polysubstituted benzofuro[2,3-c]pyridines by three-component is developed. It provides a flexible and rapid synthetic route for the construction of benzofuro[2,3-c]pyridines under mild and metal-free reaction conditions in moderate to good yields (up to 83%).

A One-Pot Chemoenzymatic Synthesis of (2S,4R)-4-Methylproline Enables the First Total Synthesis of Antiviral Lipopeptide Cavinafungin B

2018 ◽  
Author(s):  
Christian R. Zwick ◽  
Hans Renata
Keyword(s):  
Total Synthesis ◽  
Natural Product ◽  
Complex Molecule ◽  
Molecular Target ◽  
Chemoenzymatic Synthesis ◽  
General Strategy ◽  
One Pot

We report an efficient ten-step synthesis of antiviral natural product cavinafungin B in 37% overall yield. By leveraging a one-pot chemoenzymatic synthesis of (2S,4R)-4-methylproline and oxazolidine-tethered (Rink-Boc-ATG-resin) SPPS methodology, the assembly of our molecular target could be conducted in an efficient manner.This general strategy could prove amenable to the construction of other natural and unnatural linear lipopeptides. The value of incorporating biocatalytic steps in complex molecule synthesis is highlighted by this work.

Metal-Free Photoredox-Catalyzed C–H/C–H Coupling of Arenes Enabled by Interrupted Pummerer Activation

2019 ◽  
Author(s):  
Miles Aukland ◽  
Mindaugas Šiaučiulis ◽  
Adam West ◽  
Gregory Perry ◽  
David Procter
Keyword(s):  
Natural Product ◽  
Selective Reduction ◽  
Cross Coupling ◽  
One Pot ◽  
Complex Molecules ◽  
Pummerer Reaction ◽  
Metal Free ◽  
Bond Forming ◽  
Coupling Partner ◽  
Bioactive Natural Product

<p>Aryl–aryl cross-coupling constitutes one of the most widely used procedures for the synthesis of high-value materials, ranging from pharmaceuticals to organic electronics and conducting polymers. The assembly of (hetero)biaryl scaffolds generally requires multiple steps; coupling partners must be functionalized before the key bond-forming event is considered. Thus, the development of selective C–H arylation processes in arenes, that side-step the need for prefunctionalized partners, is crucial for streamlining the construction of these key architectures. Here we report an expedient, one-pot assembly of (hetero)biaryl motifs using photocatalysis and two non-prefunctionalized arene partners. The approach is underpinned by the activation of a C–H bond in an arene coupling partner using the interrupted Pummerer reaction. A unique pairing of the organic photoredox catalyst and the intermediate dibenzothiophenium salts enables highly selective reduction in the presence of sensitive functionalities. The utility of the metal-free, one-pot strategy is exemplified by the synthesis of a bioactive natural product and the modification of complex molecules of societal importance.</p>

Synthesis of Pyrrolo[1,2-a][1,6]- and [1,8]naphthyridines by Alkyne-Carbonyl Metathesis

Synthesis ◽  
2020 ◽  
Author(s):  
Peter Ehlers ◽  
Peter Langer ◽  
Marian Blanco Ponce ◽  
Silvio Parpart ◽  
Alexander Villinger ◽  
...  
Keyword(s):  
Heterocyclic Compounds ◽  
Metathesis Reaction ◽  
Synthetic Methodology ◽  
Facile Synthesis ◽  
Reaction Conditions ◽  
One Pot ◽  
Metal Free ◽  
Modular Synthesis

AbstractA concise and modular synthesis of pyrrolo[1,2-a][1,6]- and [1,8]naphthyridines by a one-pot two-step reaction consisting of electrophilic acylation followed by an alkyne-carbonyl-metathesis reaction as the final cyclization step is reported. This developed synthetic methodology allows the facile synthesis of these heterocyclic core structures in mainly high overall yields under metal-free conditions. Reaction conditions are carefully optimized and display a novel supplement to access these tricyclic heterocyclic compounds.

One-pot transition-metal free transamidation to sterically hindered amides

2018 ◽  
Vol 5 (20) ◽  
pp. 2950-2954 ◽  
Author(s):  
Weijie Guo ◽  
Jingjun Huang ◽  
Hongxiang Wu ◽  
Tingting Liu ◽  
Zhongfeng Luo ◽  
...  
Keyword(s):  
Transition Metal ◽  
Good Yield ◽  
One Pot ◽  
Metal Free ◽  
Highly Efficient ◽  
Sterically Hindered

A highly efficient one-pot transamidation of primary amides has been developed under transition-metal free conditions, generating a variety of amides including hindered amides in good yield (up to 86%) catalyzed by CsF.

scholarly journals Straightforward Strategies for the Preparation of NH-Sulfox­imines: A Serendipitous Story

Synlett ◽  
2017 ◽  
Vol 28 (19) ◽  
pp. 2525-2538 ◽  
Author(s):  
James Bull ◽  
Renzo Luisi ◽  
Leonardo Degennaro
Keyword(s):  
Transition Metal ◽  
Physicochemical Properties ◽  
Direct Synthesis ◽  
Transition Metal Catalysts ◽  
Hypervalent Iodine ◽  
Reaction Conditions ◽  
One Pot ◽  
Metal Free ◽  
Recent Developments ◽  
New Procedures

Sulfoximines are emerging as valuable new isosteres for use in medicinal chemistry, with the potential to modulate physicochemical properties. Recent developments in synthetic strategies have made the unprotected ‘free’ NH-sulfoximine group more readily available, facilitating further study. This account reviews approaches to NH-sulfoximines, with a focus on our contribution to the field. Starting from the development of catalytic strategies involving transition metals, more sustainable metal-free processes have been discovered. In particular, the use of hypervalent iodine reagents to mediate NH-transfer to sulfoxides is described, along with an assessment of the substrate scope. Furthermore, a one-pot strategy to convert sulfides directly into NH-sulfoximines is discussed, with N- and O-transfer occurring under the reaction conditions. Mechanistic evidence for the new procedures is included as well as relevant synthetic applications that further exemplify the potential of these approaches.1 Introduction2 Strategies to Form NH-Sulfoximines Involving Transition-Metal Catalysts3 Metal-Free Strategies to Prepare NH-Sulfoximines4 Mechanistic Evidence for the Direct Synthesis of NH-Sulfoximines from Sulfoxides and Sulfides5 Further Applications6 Conclusion

scholarly journals Tandem Triphosgene-Assisted Metal-Free One-pot Preparation of Nitriles and Amides from Aldehydes and Ketones

2021 ◽  
Author(s):  
Jianguo liu ◽  
Xiu-Zhi Wei ◽  
Longlong Ma
Keyword(s):  
Metal Catalysts ◽  
Organic Base ◽  
Reaction Conditions ◽  
One Pot ◽  
Metal Free ◽  
Aldehydes And Ketones ◽  
Ester Linkage ◽  
Hydrolysis Of ◽  
By Products

Here we report a facile and efficient triphosgene-assisted one-pot conversion of aldehydes/ketones into nitriles/amides. The triphosgene, a kind of phosgene alternative, containing both ester linkage and chloromethyl units, easily reacts with oximes for the preparation of nitriles/amides. However, the reaction of oximes with triphosgene can’t fully convert corresponding nitriles/amides due to hydrolysis of oximes to aldehydes or ketones. Our protocol tandem proceeds smoothly without the use of organic base and metal catalysts. Diverse functionalized aromatic, aliphatic, and allylic aldehydes/ketones incorporating biomass-derived platform compounds were successfully converted to nitriles and amides in excellent yields. Compared to step-by-step reaction, this tandem strategy is characterized by multi-step reaction in one pot, mild reaction conditions, and fewer by-products.

A transition metal-free approach to a regioselective total synthesis of the natural product derivative 6-methylellipticine, a potent anticancer agent

2019 ◽  
Vol 60 (51) ◽  
pp. 151309 ◽  
Author(s):  
Song-Bo Lin ◽  
Wan-Wan Wang ◽  
Jin-Peng Meng ◽  
Xi-Wang Li ◽  
Jun Wu ◽  
...  
Keyword(s):  
Transition Metal ◽  
Total Synthesis ◽  
Natural Product ◽  
Anticancer Agent ◽  
Metal Free

scholarly journals One-Pot, Metal-Free Synthesis of Dimethyl Carbonate from CO2 at Room Temperature

2020 ◽  
Vol 1 (3) ◽  
pp. 298-314
Author(s):  
Santosh Govind Khokarale ◽  
Thai Q. Bui ◽  
Jyri-Pekka Mikkola
Keyword(s):  
Ionic Liquid ◽  
Room Temperature ◽  
Dimethyl Carbonate ◽  
High Selectivity ◽  
Chemical Species ◽  
Side Reactions ◽  
Ambient Conditions ◽  
Reaction Conditions ◽  
One Pot ◽  
Metal Free

Herein, we report on the metal-free, one-pot synthesis of industrially important dimethyl carbonate (DMC) from molecular CO2 under ambient conditions. In this process, initially the CO2 was chemisorbed through the formation of a switchable ionic liquid (SIL), [DBUH] [CH3CO3], by the interaction of CO2 with an equivalent mixture of organic superbase 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) and methanol. The obtained SIL further reacted with methyl iodide (CH3I) to form DMC. The synthesis was carried out in both dimethyl sulfoxide (DMSO) and methanol. Methanol is preferred, as it not only served as a reagent and solvent in CO2 capture and DMC synthesis, but it also assisted in controlling the side reactions between chemical species such as CH3I and [DBUH]+ cation and increased the yield of DMC. Hence, the use of methanol avoided the loss of captured CO2 and favored the formation of DMC with high selectivity. Under the applied reaction conditions, 89% of the captured CO2 was converted to DMC. DBU was obtained, achieving 86% recovery of its salts formed during the synthesis. Most importantly, in this report we describe a simple and renewable solvent-based process for a metal-free approach to DMC synthesis under industrially feasible reaction conditions.

A One-Pot Chemoenzymatic Synthesis of (2S,4R)-4-Methylproline Enables the First Total Synthesis of Antiviral Lipopeptide Cavinafungin B

2018 ◽  
Author(s):  
Christian R. Zwick ◽  
Hans Renata
Keyword(s):  
Total Synthesis ◽  
Natural Product ◽  
Complex Molecule ◽  
Molecular Target ◽  
Chemoenzymatic Synthesis ◽  
General Strategy ◽  
One Pot

We report an efficient ten-step synthesis of antiviral natural product cavinafungin B in 37% overall yield. By leveraging a one-pot chemoenzymatic synthesis of (2S,4R)-4-methylproline and oxazolidine-tethered (Rink-Boc-ATG-resin) SPPS methodology, the assembly of our molecular target could be conducted in an efficient manner.This general strategy could prove amenable to the construction of other natural and unnatural linear lipopeptides. The value of incorporating biocatalytic steps in complex molecule synthesis is highlighted by this work.

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