The synthesis and application of [3.3.0]furofuranone species has received considerable attention from the scientific community. During the last twenty years, there has been a remarkable increase in publications focusing on their relevant method development as well as applications to natural product synthesis. This tutorial review discusses instructive examples to give a special emphasis on the development of new synthetic approaches and important applications to the total synthesis of natural products.

An enantioselective rhodium(I)‐catalyzed Pauson–Khand reaction (PKR) using 1,6‐chloroenynes that contain challenging 1,1‐disubstituted olefins is described. In contrast to the previous studies with these types of substrates, which are only suitable for a single type of tether and alkyne substituent, the new approach results in a more expansive substrate scope, including carbon and heteroatom tethers with polar and non‐polar substituents on the alkene. DFT calculations provide critical insight into the role of the halide, which pre‐polarizes the alkyne to lower the barrier for metallacycle formation and provides the proper steric profile to promote a favorable enantiodetermining interaction between substrate and chiral diphosphine ligand. Hence, the chloroalkyne enables the efficient and enantioselective PKR with 1,6‐enynes that contain challenging 1,1‐disubstituted olefins, thereby representing a new paradigm for enantioselective reactions involving 1,6‐enynes.

An enantioselective rhodium(I)‐catalyzed Pauson–Khand reaction (PKR) using 1,6‐chloroenynes that contain challenging 1,1‐disubstituted olefins is described. In contrast to the previous studies with these types of substrates, which are only suitable for a single type of tether and alkyne substituent, the new approach results in a more expansive substrate scope, including carbon and heteroatom tethers with polar and non‐polar substituents on the alkene. DFT calculations provide critical insight into the role of the halide, which pre‐polarizes the alkyne to lower the barrier for metallacycle formation and provides the proper steric profile to promote a favorable enantiodetermining interaction between substrate and chiral diphosphine ligand. Hence, the chloroalkyne enables the efficient and enantioselective PKR with 1,6‐enynes that contain challenging 1,1‐disubstituted olefins, thereby representing a new paradigm for enantioselective reactions involving 1,6‐enynes.