Transition Metal-Catalyzed Synthesis of Alkenes and Dienes

The synthesis of alkenes and dienes via transition metal catalysis has transformed organic chemistry by enabling efficient access to unsaturated building blocks with high selectivity. Strategies such as metal-catalysed cross-coupling, C–H activation, olefin metathesis and hydrofunctionalisation allow precise installation of carbon–carbon double bonds under mild conditions. Palladium, nickel, ruthenium and iron catalysts dominate the field, offering modular routes to tetrasubstituted olefins, conjugated dienes and complex polyenes. Advances in directing-group design and catalytic cycle engineering have improved regio- and stereocontrol, reducing steps and waste. These methodologies underpin the manufacture of pharmaceuticals, agrochemicals and advanced materials by affording stereodefined networks, enhancing biological activity and material properties. As sustainability rises in priority, the development of earth-abundant metal catalysts and solvent-economic processes is broadening the environmental and economic viability of these transformations.

Research from Nature Portfolio

Recent studies have demonstrated innovative C–H functionalisation pathways to construct complex alkenes. The introduction of a remote carbonyl directing group has enabled a sequential Heck-type coupling, alkene isomerisation and C(sp2)–H arylation sequence under palladium catalysis, affording stereodefined tetrasubstituted olefins in high yields. By leveraging reversible E/Z isomerisation and vicinal C–H arylation, this strategy achieves precise stereocontrol without harsh conditions. Complementary work has revealed geminal olefinic C–H activation via four- to eight-membered exo-metallocycle intermediates. Weak O-monodentate coordination directs palladium into remote positions on alkenyl substrates, expanding the repertoire of accessible olefins and enabling late-stage modification of complex molecules.

Transition Metal-Catalyzed Synthesis of Alkenes and Dienes publication trend

The graph below shows the total number of articles in transition metal-catalyzed synthesis of alkenes and dienes across all publications each year (not limited to Nature Index journals).

Technical terms

Heck reaction: Palladium-catalysed coupling of alkenes with aryl or vinyl halides.

C–H activation: Direct cleavage of a carbon–hydrogen bond by a metal catalyst to form a new bond.

Metallocycle: Cyclic organometallic intermediate in which the metal centre is incorporated into a ring.

Conjugated diene: Molecule featuring two alternating double bonds that enable electron delocalisation.

Stereoselectivity: Preferential formation of one stereoisomer over others in a chemical reaction.

References

1. Remote-carbonyl-directed sequential Heck/isomerization/C(sp2)–H arylation of alkenes for modular synthesis of stereodefined tetrasubstituted olefins. Nature Communications (2024).
2. Geminal group-directed olefinic C-H functionalization via four- to eight-membered exo-metallocycles. Nature Communications (2019).
3. Ruthenium-catalyzed formal sp 3 C–H activation of allylsilanes/esters with olefins: efficient access to functionalized 1,3-dienes. Chemical Science (2021).
4. Iron-Catalyzed Cross-Coupling of α‑Allenyl Esters with Grignard Reagents for the Synthesis of 1,3-Dienes. Organic Letters (2023).
5. Synthesis of highly substituted 1,3-dienes through halonium promoted 1,2-sulfur migration of propargylic thioethers. Chemical Communications (2024).