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46.6.3 Method 3: Synthesis of 1,3-Dienes by Palladium-Catalyzed Cross-Coupling Reactions

DOI: 10.1055/sos-SD-046-00149

Negishi, E.; Wang, G.Science of Synthesis, (200946256.

Despite the development of some highly selective and efficient syntheses of stereo- and regiodefined 1,3-dienes via stoichiometric migratory insertion (Section 46.6.1) and cyclic carbometalation (Section 46.6.2) with boron, titanium, zirconium, and other metals, the overall synthetic scope and value of the seemingly most straightforward [2C+2C] routes to 1,3-dienes had been dwarfed by the conventional [1C+3C] processes represented by the Wittig and related carbonyl alkenation (olefination) reactions until the advent of the palladium-catalyzed cross-coupling reactions of stereo- and regiodefined alkenylmetals containing aluminum, zirconium, or zinc (widely known as the Negishi coupling) discovered during the 19761978 period (Schemes 20 and 21).[‌75‌‌77‌] Together with the subsequently developed Suzuki version of the palladium-catalyzed alkenylboronalkenyl electrophile coupling reported first in 1979,[‌78‌] these palladium-catalyzed alkenylalkenyl coupling processes currently represent the most widely applicable and highly (mostly 98%) selective [2C+2C] route to 1,3-dienes. The corresponding reaction of alkenylstannanes (Stille protocol), developed since the mid-1980s,[‌79‌] has also been widely used.[‌80‌] However, its synthetic scope is relatively limited owing to the intrinsically low reactivity of alkenylstannanes, and the inherent toxicity associated with tin is a serious concern. Although much less widely used, the corresponding reactions of organometals containing magnesium,[‌81‌] copper,[‌82‌,‌83‌] silicon,[‌84‌‌86‌] indium,[‌87‌,‌88‌] and others should also be noted.

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References


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