Stereoselective construction of conjugated dienes and polyenes has remained an enduring synthetic problem, due to the central roles they play in natural product synthesis, methodology, and medicine. This review focuses on the recent developments in dienylation as an emerging strategy for the direct installation of unsaturated four carbon atom units of conjugated π-systems, outlining the regio- and stereoselectivity, as well as the synthetic scope of reactions with various dienylating reagents and the mechanistic implications of the catalytic cross-coupling processes that are used to enable dienylation.
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http://dx.doi.org/10.1055/a-1924-2564 | DOI Listing |
Toxins (Basel)
December 2024
Department of Chemistry, University of Ghana, Legon-Accra P.O. Box LG56, Ghana.
Mycolactone is a complex macrolide toxin produced by , the causative agent of Buruli ulcer. The aim of this paper is to review the chemistry, biosynthetic, and synthetic pathways of mycolactone A/B to help develop an understanding of the mode of action of these polyketides as well as their therapeutic potential. The synthetic work has largely been driven by the desire to afford researchers enough (≥100 mg) of the pure toxins for systematic biological studies toward understanding their very high biological activities.
View Article and Find Full Text PDFChem Asian J
December 2024
CSIR National Chemical Laboratory, Center for Materials Characterization, INDIA.
We present a comprehensive account of our efforts directed towards the synthesis of sacubitril, a neprilysin inhibitor used in combination with valsartan and marketed as Entresto™. Our initial approach to the formal synthesis of sacubitril employed a chiral pool strategy, utilizing (S)-pyroglutamic acid as a key building block and Cu(I)-mediated Csp2-Csp3 cross-coupling as a key transformation. Further investigations led to the development of chiral amine transfer (CAT) reagents-based stereoselective synthesis.
View Article and Find Full Text PDFTransition metal-catalyzed carbocyclization reactions provide a powerful method for the stereoselective assembly of complex, highly substituted (poly)cyclic scaffolds. Although 1,6-enynes are common substrates for these transformations, using polysubstituted alkene derivatives to construct functionalized cyclic products remains challenging due to their significantly lower reactivity. This highlights key developments in stereoselective semi-intramolecular metal-catalyzed [(2+2)+1] and [(2+2)+2] carbocyclizations of 1,6-enynes containing 1,1-disubstituted alkenes, which produce cycloadducts with quaternary stereogenic centers.
View Article and Find Full Text PDFChem Rec
December 2024
Department of Pharmacy, The Second Affiliated Hospital of Army Medical University, Chongqing, 400037, China.
The catalytic asymmetric allylation reaction involving allylboron species has emerged as a powerful tool to access highly stereoselective allylation products. In the early years, most of the researches focused on the reaction of unsubstituted allylboronates with ketones or imines. With the synthesis of complex substituted allylboronates, allylboronic acids and allyltrifluoroborates, the type of reactions and the variety of substrates are greatly expanded.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, and Chemical Biology Center, Peking University, 38 Xueyuan Road, Beijing 100191, China.
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