American Chemical Society
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Paterno−Büchi Coupling of (Diaryl)acetylenes and Quinone via Photoinduced Electron Transfer

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journal contribution
posted on 1998-01-21, 00:00 authored by E. Bosch, S. M. Hubig, J. K. Kochi
Photoinduced coupling of an acetylene with a quinone in two wavelength regions (λDB and λCT) can be regioselective to yield a single quinone methide adduct when various diarylacetylenes (DA) and 2,6-dichlorobenzoquinone (DB) are used. Thus, the direct photoexcitation of DB at λDB = 355 nm or the specific activation of the 1:1 electron donor−acceptor complex [DA,DB] at λCT = 532 nm both lead to the transient ion-radical pair [DA•+,DB•-], which is established by time-resolved (ps,ns) spectroscopy. Competition between back electron transfer (kBET) and ion-radical pair collapse (kC) to the distonic adduct DA-DB, as described in Schemes and , limits the quantum yields for both photochemical processes in Table . The biradical nature of the distonic adduct in Scheme accommodates the various facets of acetylene reactivity and unique regioselectivity to yield the same quinone methide by both actinic processes. In a more general context, the electron-transfer mechanism established by the charge-transfer excitation of [DA,DB] provides compelling evidence that the Paterno−Büchi coupling (by direct excitation of DB) can proceed via the same sequence of reactive intermediates.