Light-driven [2+2] cycloaddition is the most direct strategy to build tetrasubstituted cyclobutanes, core components of many lead compounds for drug development. Significant advances in the chemoselectivity and enantioselectivity of [2+2] photocycloadditions have been made, but exceptional and tunable diastereoselectivity and regioselectivity (head-to-head vs. head-to-tail adducts), required for synthesis of bioactive molecules, have not yet been achieved. Here we show that colloidal quantum dots (QDs) serve as visible-light chromophores, photocatalysts, and reusable scaffolds for homo-and hetero-intermolecular [2+2] photocycloadditions of 4vinylbenzoic acid derivatives, including aryl-conjugated alkenes, with up to 98% switchable regioselectivity and 98% diastereoselectivity for the previously minor syn-cyclobutane products, including the syn-head-to-tail cyclobutane, which has never before been accessed as the major product of a hetero-photocycloaddition. Transient absorption spectroscopy confirms that our system is the first example of catalysis triggered by triplet-triplet energy transfer from a QD. The precisely controlled triplet energy levels of QD photocatalysts facilitate efficient and selective heterocoupling, a major challenge in direct cyclobutane synthesis.Light-driven [2+2] cycloadditions 1-5 , simple routes to complex, biologically relevant tetrasubstituted cyclobutanes [6][7][8] , follow several possible excited-state routes. Those that proceed through the triplet excited state of the reagent olefin are advantageous because (i) their scope is not limited by the electrochemical potentials of the substrate, (ii) triplets have long enough lifetimes to mediate intermolecular cycloadditions, and (iii) triplets are accessible with visible light through excitation of a triplet sensitizer, such as a transition metal complex or organic chromophore 9 , followed by triplet-triplet energy transfer (TT Users may view, print, copy, and download text and data-mine the content in such documents, for the purposes of academic research, subject always to the full Conditions of use:http://www.nature.com/authors/editorial_policies/license.html#termsReprints and permissions information is available at http://www.nature.com/reprints.

This Article describes the design of a colloidal quantum dot (QD) photosensitizer for the Pd-photocatalyzed Heck coupling of styrene and iodocyclohexane to form 2-cyclohexylstyrene. In the presence of 0.05 mol % CdS QDs, which have an emission spectrum that overlaps the absorption spectrum of a key Pd­(II)­alkyl iodide intermediate, the reaction proceeds with 82% yield for the Heck product at 0.5 mol % loading of Pd catalyst; no product forms at this loading without a sensitizer. A radical trapping experiment and steady-state and transient optical spectroscopies indicate that the QDs transfer energy to a Pd­(II)­alkyl iodide intermediate, pushing the reaction toward a Pd­(I) alkyl radical species that leads to the Heck coupled product, and suppressing undesired β-hydride elimination directly from the Pd­(II)­alkyl iodide. Functionalization of the surfaces of the QDs with isonicotinic acid increases the rate constant of this reaction by a factor of 2.4 by colocalizing the QD and the Pd-complex. The modularity and tunability of the QD core and surface make it a convenient and effective chromophore for this alternative mode of cooperative photocatalysis.

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This paper describes spectroscopic evidence for the photoinduced transfer of a hole from the biexcitonic state of a CdS quantum dot (QD) to a phenothiazine (PTZ) molecular acceptor, covalently linked to the QD through phenyldithiocarbamate (PTC), with power-dependent yields of 8–21%. Visible and near-infrared transient absorption spectroscopy (TA) data suggest that the mechanisms of hole extraction include direct hole transfer from the QD’s valence band to PTZ in 2.4 ± 0.2 ps, or trapping of holes at the QD surface in ∼1 ps, followed by sequential hole transfer to PTZ. Both of these mechanisms potentially out-compete Auger recombination of biexcitonic states, which occurs within these QDs in 20 ± 1 ps. These results suggest that the PTC linkage will be useful for extracting multiple holes from a QD photosensitizer or solo photocatalyst to drive multistep oxidation reactions.

This Communication describes the use of CuInS 2 / ZnS quantum dots (QDs) as photocatalysts for the reductive deprotection of aryl sulfonyl-protected phenols. For a series of aryl sulfonates with electron-withdrawing substituents, the rate of deprotection for the corresponding phenyl aryl sulfonates increases with decreasing electrochemical potential for the two electron transfers within the catalytic cycle. The rate of deprotection for a substrate that contains a carboxylic acid, a known QD-binding group, is accelerated by more than a factor of ten from that expected from the electrochemical potential for the transformation, a result that suggests that formation of metastable electron donor-acceptor complexes provides a significant kinetic advantage. This deprotection method does not perturb the common NHBoc or toluenesulfonyl protecting groups and, as demonstrated with an estrone substrate, does not perturb proximate ketones, which are generally vulnerable to many chemical reduction methods used for this class of reactions.