The catalytic performance of cinchonidine in the promotion of thiol additions to conjugated ketones was used as a probe to assess the tethering of molecular functionality onto solid surfaces using well-known "click" chemistry involving easy-to-react linkers. It has been assumed in many applications that the tethered molecules retain their chemical properties and dominate the chemistry of the resulting solid systems, but it is shown here that this is not always the case. Indeed, a loss of enantioselectivity was observed upon tethering, which could be accounted for by a combination of at least three effects: (1) the nonselective catalytic activity of the surface of the solid itself; (2) the activity of the OH species generated by hydrolysis of some of the Si-alkoxy groups in the trialkoxy moieties used to bind many linkers to oxide surfaces; and (3) the bonding of the molecule to be tethered directly to the surface. Several ideas were also tested to minimize these problems, including the silylation of the active OH groups within the surface of the oxide support, the selection of solvents to optimize silane polymerization and minimize their breaking up via hydrolysis or alcoholysis reactions, and the linking at defined positions in the molecule to be tethered in order to minimize its ability to interact with the surface.

Cinchonidine, a naturally occurring cinchona alkaloid, was tethered to a high-surface-area silica substrate in order to create a new solid chiral catalyst. Two synthetic routes were explored for this grafting, relying on the use of an intermediate linker and so-called ''click'' chemistry. Both routes proved viable, but the procedure where cinchonidine is first derivatized with 3-isocyanatopropyltriethoxysilane (ICPTEOS) at the alcohol position and the resulting product then anchored to the silica surface was deemed the most efficient. Bonding to the surface occurs via the formation of Si-O-Si bonds, on average two out of the three possible per cinchonidine, and takes place preferentially at silica surface sites with two geminal hydroxyl groups on the same silicon atom. Approximately 10% of the available OH surface groups are derivatized in this procedure. The resulting catalyst was successfully tested for the addition of aromatic thiols to unsaturated ketones, a reaction promoted by amines (the tertiary quinuclidine nitrogen atom in the case of cinchonidine). The activity of the supported cinchonidine proved comparable to that of the free molecule, but tethering does lead to a significant loss in enantioselectivity.

Useful tetrahydropyran units such as 3 can be prepared with high diastereoselectivity (d.r.>30:1). A key step is the catalytic asymmetric allyl‐transfer reaction from 1 to achiral aldehydes catalyzed by [{(R)‐binol}TiIV{OCH(CF3)2}2] to give 2 (90–97 % ee). A second allyl‐transfer reaction from 2 to a carbonyl compound leads to 3. binol=2,2′‐binaphthol.

A strategy has been devised to add molecular functionality to heterogeneous catalysts in a spatially correlated fashion.

A new selective hydrocarbon oxidation heterogeneous catalyst has been developed by tethering an iron-coordinated cavitand to the surfaces of a SBA-15 mesoporous material. The resulting material was shown to catalyze the oxidation of cyclic hydrocarbons at room temperature and to be quite robust and easily recyclable. The role of the cavitand scaffold is to prevent the catalytic Fe ions from interacting directly with the silica surface and to provide a controlled environment for reversible redox catalysis. An induction period is required for the activation of the catalyst, during which a change in coordination of the iron ions to the tethered cavitand takes place.