Substrate Channeling in Compartmentalized Nanoreactors

Thermo- and photoresponsive nanoreactors based on shell cross-linked micelles (SCMs) for the rhodium-catalyzed asymmetric transfer hydrogenation (ATH) of ketones have been developed from poly(2-oxazoline) triblock terpolymers. The nanoreactors incorporate thermoresponsive poly(2-isopropyl-2-oxazoline) as the hydrophilic corona and are covalently cross-linked with a photoswitchable spiropyran molecule. UV irradiation or changes in temperature trigger morphology switching of the polymer-based nanoreactors that alters the hydrophobicity in separate layers of the SCMs, resulting in dynamic substrate selectivity of the ATH in water. Control experiments and kinetic studies show that the thermoresponsive outer layer induces the gated behavior for more hydrophobic substrates, whereas the photoresponsive cross-linking layer induces the gated behavior for less hydrophobic substrates. The nanoreactors mimic the multichannels in Nature, transporting substrates and reagents into the catalytic core which can be controlled through external triggers such as temperature and light wavelengths. Additionally, the nanoreactors can be easily recovered and reused with continued high activity and selectivities.