This account surveys the current progress on the application of intra- and intermolecular enyne metathesis as main key steps in the synthesis of challenging structural motifs and stereochemistries found in bioactive compounds. Special emphasis is placed on ruthenium catalysts as promoters of enyne metathesis to build the desired 1,3-dienic units. The advantageous association of this approach with name reactions like Grignard, Wittig, Diels-Alder, Suzuki-Miyaura, Heck cross-coupling, etc. is illustrated. Examples unveil the generality of such tandem reactions in providing not only the intricate structures of known, in vivo effective substances but also for designing chemically modified analogs as valid alternatives for further therapeutic agents.
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http://dx.doi.org/10.3762/bjoc.16.68 | DOI Listing |
J Org Chem
December 2024
College of Chemistry and Chemical Engineering, Shaanxi University of Science and Technology, Xi'an 710021, P. R. China.
Org Biomol Chem
August 2024
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai-400076, India.
Herein, we present a general approach for synthesizing pluramycin hybrids, which are analogous to the pluramycinone carbocyclic skeleton. This method involves a sequence of relay ring-closing enyne metathesis, Diels-Alder and oxidative aromatization reactions to synthesize pluramycinone-sugar hybrids. As part of our ongoing research, we have successfully synthesized two pluramycin hybrid analogues by carefully monitoring the late-stage oxidative aromatization steps, which depend on the stereo-orientation of the Diels-Alder cycloadduct at the C-4 center.
View Article and Find Full Text PDFOrg Lett
August 2024
Key Laboratory of Jiangxi Province for Persistent Pollutants Control and Resources Recycle, Nanchang Hangkong University, Nanchang 330063, People's Republic of China.
A photocatalytic method for the ring-closing 1,7-enyne metathesis using the α-amino radical as an alkene deconstruction auxiliary is present. Preliminary mechanistic studies suggest that intramolecular 1,5-hydrogen atom transfer is the key to the generation and β-scission of the α-amino radical, while the dearomatization of arenes and ring opening of cyclopropanes are the key to construct spirocyclic quinolin-2-ones. This approach highlights the potential of ring-closing 1,7-enyne metathesis, providing a green, efficient, and step-economical way for the synthesis of spirocyclic quinolin-2-ones.
View Article and Find Full Text PDFJ Org Chem
August 2024
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
Herein, we report the first asymmetric total synthesis of 4-hydroxy-8--methyltetrangomycin (), 4-hydroxytetrangomycin (), and 4-keto-8--methyltetrangomycin (), angucyclinones featuring a highly oxidized nonaromatic A ring. A sequential enyne metathesis/Diels-Alder approach was utilized successfully to construct the tetracyclic skeleton of the angucyclinones. Late-stage acetonide deprotection challenges were overcome by A ring functional group manipulation, yielding a dihydroxy intermediate prior to the benzylic photo-oxidation, facilitating the total syntheses of angucyclinones -.
View Article and Find Full Text PDFChemistry
September 2024
Department of Chemistry, Chungbuk National University, 1 Chungdae-ro, Seowon-gu, Cheongju, 28644, Republic of Korea.
The precise synthesis of chiral polymers remains a significant challenge in polymer chemistry, particularly for applications in advanced biomedical and electronic materials. The development of degradable polymers is important for eco-friendly and advanced materials. Here, we introduce a stereo-controlled degradable polymer via cascade enyne metathesis polymerization and enantioselective acetal synthesis through Pd-catalyzed asymmetric hydroamination.
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