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 (E) 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 (E) and (Z) olefins from the same reaction partners, are discussed.

Department of Chemical Biology Faculty of Science Palacky University Šlechtitelů 27 779 00 Olomouc Czech Republic

Department of Organic Chemistry Faculty of Science Palacky University 17 Listopadu 779 00 Olomouc Czech Republic

Laboratory of Growth Regulators Palacky University and Institute of Experimental Botany AS CR Šlechtitelů 27 779 00 Olomouc Czech Republic

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