Control of silver(I)-dialkyl chalcogenide coordination by a synthetic cavity.

The discrete cavity of a self-assembled palladium-tris(4-pyridyl)triazine cage dictates the ratio of metal, ligand, and a non-coordinative molecule in the formation of silver(I)-dialkyl chalcogenide (Et, nBu; S, Se) complexes and defines their coordination arrangement.

Metal-organic proximity in a synthetic pocket.

Proximity between a noninteractive organic substrate and a transition metal (trans-MCl2(PEt3)2; M = Pd or Pt) is achieved by their co-encapsulation within a synthetic cage, as revealed by X-ray crystallographic analysis and NOESY experiments. Through co-encapsulation with a Pd(II) complex, a terminal alkyne was activated within the cage to give a σ-alkynylpalladium complex.

A self-assembled cage as a non-covalent protective group: regioselectivity control in the nucleophilic substitution of aryl-substituted allylic chlorides.

Aryl-substituted allylic chlorides are accommodated by a self-assembled cage in such a restricted orientation that the internal reaction sites are shielded while the external ones are exposed. This non-covalent protection enhances terminal regioselectivity in the allylic substitution.

Synthesis of 1,2-bisalkylidenecyclopentanes from 1,6-allenynes via stereoselective addition of nucleophiles to ruthenacyclopentenes.

Ruthenium-catalyzed cyclization of 1,6-allenynes occurs via the addition of heteroatom nucleophiles to ruthenacyclopentenes, providing functionalized 1,2-bisalkylidenecyclopentanes in a highly regio- and stereoselective manner.