A relay energy transfer paradigm for asymmetric photocatalyzed [4+2] cycloadditions.
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| Title: | A relay energy transfer paradigm for asymmetric photocatalyzed [4+2] cycloadditions. |
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| Authors: | Wang, Yong-Bin (AUTHOR), Xu, Yi-An (AUTHOR), Li, Cheng (AUTHOR), Cheng, Gang-Ya (AUTHOR), Xiang, Shao-Hua (AUTHOR), Tan, Bin (AUTHOR) |
| Source: | Science. 5/21/2026, Vol. 392 Issue 6800, p850-857. 8p. |
| Subjects: | Energy transfer, Asymmetric synthesis, Ring formation (Chemistry), Photocatalysis |
| Abstract: | In asymmetric energy transfer photocatalysis, direct incorporation of conventional chiral catalysts has achieved satisfactory enantiocontrol in several transformations. However, the efficiency and even feasibility of this mode are still limited by the energy transfer barrier that arises from the inevitable catalyst-mediated spatial segregation. To overcome this underappreciated constraint, we designed a relay energy transfer catalytic mode in which the catalyst acts as a bridge for energy transfer between the photosensitizer and the substrate. Guided by this concept, we engineered a class of chiral energy transfer acid catalysts capable of delivering high triplet energy. These catalysts effectively circumvent the inherent stoichiometric dependence on acid activators in dearomative [4+2] cyclization between quinolines and alkenes. The tunability of side arms and the proximity of the catalytic site to the chiral source optimize regio-, diastereo-, and enantioselectivities. Editor's summary: There has recently been great progress in using light-absorbing photocatalysts to drive a variety of chemical reactions. However, a persisting challenge is the need to simultaneously optimize the catalyst for its light-absorbing properties and its selectivity properties. Wang et al. have introduced a second, bridging catalyst that can help to channel energy from the light absorber to the substrate while also inducing stereoselectivity. Enantioselective cycloaddition of triplet-excited quinolines to alkenes showcases the technique. —Jake S. Yeston [ABSTRACT FROM AUTHOR] |
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| Database: | Psychology and Behavioral Sciences Collection |
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| Abstract: | In asymmetric energy transfer photocatalysis, direct incorporation of conventional chiral catalysts has achieved satisfactory enantiocontrol in several transformations. However, the efficiency and even feasibility of this mode are still limited by the energy transfer barrier that arises from the inevitable catalyst-mediated spatial segregation. To overcome this underappreciated constraint, we designed a relay energy transfer catalytic mode in which the catalyst acts as a bridge for energy transfer between the photosensitizer and the substrate. Guided by this concept, we engineered a class of chiral energy transfer acid catalysts capable of delivering high triplet energy. These catalysts effectively circumvent the inherent stoichiometric dependence on acid activators in dearomative [4+2] cyclization between quinolines and alkenes. The tunability of side arms and the proximity of the catalytic site to the chiral source optimize regio-, diastereo-, and enantioselectivities. Editor's summary: There has recently been great progress in using light-absorbing photocatalysts to drive a variety of chemical reactions. However, a persisting challenge is the need to simultaneously optimize the catalyst for its light-absorbing properties and its selectivity properties. Wang et al. have introduced a second, bridging catalyst that can help to channel energy from the light absorber to the substrate while also inducing stereoselectivity. Enantioselective cycloaddition of triplet-excited quinolines to alkenes showcases the technique. —Jake S. Yeston [ABSTRACT FROM AUTHOR] |
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| ISSN: | 00368075 |
| DOI: | 10.1126/science.aeb8506 |
