Since its discovery, the Julia-Kocienski olefination reaction has over past 30 years become one of the key C-C connective methods that is used in late-stage natural product synthesis. The reaction proceeds under mild reaction conditions, with a wide substrate scope and functional group tolerance range and with high () selectivity. In this focused review, we discuss the reaction from a mechanistic point of view and disclose key features that play an important role in reaction selectivity. Finally, the mechanistic aspects of the newly developed modification of the Julia-Kocienski reaction, which allows the formation of both () and () olefins from the same reaction partners, are discussed.
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http://dx.doi.org/10.3390/molecules29122719 | DOI Listing |
Angew Chem Int Ed Engl
December 2024
Department of Chemistry and Chemical Biology, Harvard University Cambridge, Massachusetts, 02138, United States.
Sulfenyl fluorides are organic compounds of sulfur in formal oxidation state +2 with the formula R-S-F. Although the chloride, bromide, and iodide analogues have been extensively described in the literature, arenesulfenyl fluorides remain essentially unstudied. These structures have been implicated as putative intermediates in established processes to access polyfluorinated sulfur species; however, definitive and direct evidence of their existence has not been obtained, nor has a systematic understanding of their reactivity.
View Article and Find Full Text PDFMolecules
August 2024
Shaanxi Key Laboratory for Catalysis, College of Chemical and Environment Science, Shaanxi University of Technology, Hanzhong 723001, China.
The tea tussock moth is a pest that damages tea leaves, affecting the quality and yield of tea and causing huge economic losses. The efficient asymmetric total synthesis of the sex pheromone of the tea tussock moth was achieved using commercially available starting materials with a 25% overall yield in 11 steps. Moreover, the chiral moiety was introduced by Evans' template and the key C-C bond construction was accomplished through Julia-Kocienski olefination coupling.
View Article and Find Full Text PDFChem Sci
July 2024
Laboratory of Asymmetric Catalysis and Synthesis, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne (EPFL) 1015 Lausanne Switzerland
The unique electronic and steric parameters of chiral cyclic alkyl amino carbene (CAAC) ligands render them appealing steering ligands for enantioselective transition-metal catalyzed transformations. Due to the lack of efficient synthetic strategies to access particularly attractive α-chiral CAACs assessment and exploitation of their full synthetic potential remain difficult. Herein, we report a streamlined strategy to assemble a library of diastereo- and enantiomerically pure CAAC ligands featuring the notoriously difficult to access α-quaternary stereogenic centers.
View Article and Find Full Text PDFOrg Biomol Chem
July 2024
Department of Organic Synthesis and Process Chemistry, CSIR-Indian Institute of Chemical Technology, Hyderabad 500007, India.
A practical and efficient synthesis of the C8-C23 fragment of antarlides A-H, incorporating six stereocenters and a conjugated diene, is reported. A strategic combination of synthetic methods, including CBS reduction, Evans' aldol reaction, Keck-Maruoka allylation, and enzymatic resolution, enabled the selective introduction of these stereocenters. Furthermore, the pivotal coupling of key fragments is successfully executed through a Julia-Kocienski olefination reaction, connecting the C8-C14 and C15-C23 subunits.
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June 2024
Department of Chemical Biology, Faculty of Science, Palacky University, Šlechtitelů 27, 779 00 Olomouc, Czech Republic.
Since its discovery, the Julia-Kocienski olefination reaction has over past 30 years become one of the key C-C connective methods that is used in late-stage natural product synthesis. The reaction proceeds under mild reaction conditions, with a wide substrate scope and functional group tolerance range and with high () selectivity. In this focused review, we discuss the reaction from a mechanistic point of view and disclose key features that play an important role in reaction selectivity.
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