Matches in SemOpenAlex for { <https://semopenalex.org/work/W2076133798> ?p ?o ?g. }
- W2076133798 endingPage "5469" @default.
- W2076133798 startingPage "5461" @default.
- W2076133798 abstract "In the Paternó-Büchi reaction of chiral p-cyanobenzoates (1) with 1,1-diphenylethene (2), we revealed that the excited charge-transfer (CT) complex formed upon selective excitation at the CT band is distinctly different in structure and reactivity from the conventional exciplex generated through the direct excitation of acceptor 1 which subsequently associates with donor 2. Thus, the favored diastereoface upon photocycloaddition, as well as the temperature- and solvent-dependent behavior of the product's diastereoselectivity, were highly contrasting, often opposite, to each other upon direct versus CT excitation. From the activation parameters obtained by the Eyring analyses of the diastereoselectivity, we are able to infer that the conventional exciplex is relatively flexible and susceptible to the environmental variants, whereas the CT complex is better pi-pi stacked and more rigid in the ground state and also in the excited state, leading to the significantly smaller differential activation enthalpies and entropies. More interestingly, the signs of the differential activation parameters determined for direct and CT excitation are consistently opposite to each other and the isokinetic temperatures calculated therefrom differ significantly, unambiguously revealing the distinctly different nature in structure and reactivity of these two excited-state complex species. Thus, the combined use of irradiation wavelength, temperature, and solvent provides us with a convenient, powerful tool not only for elucidating the mechanistic details of photoreaction but also for critically controlling the stereochemical outcomes of photochirogenic reaction." @default.
- W2076133798 created "2016-06-24" @default.
- W2076133798 creator A5040529877 @default.
- W2076133798 creator A5086349914 @default.
- W2076133798 creator A5091175594 @default.
- W2076133798 date "2010-07-27" @default.
- W2076133798 modified "2023-10-17" @default.
- W2076133798 title "Solvent and Temperature Effects on Diastereodifferentiating Paternó−Büchi Reaction of Chiral Alkyl Cyanobenzoates with Diphenylethene upon Direct versus Charge-Transfer Excitation" @default.
- W2076133798 cites W131283666 @default.
- W2076133798 cites W1503020075 @default.
- W2076133798 cites W1545653090 @default.
- W2076133798 cites W1963737263 @default.
- W2076133798 cites W1963764833 @default.
- W2076133798 cites W1964678992 @default.
- W2076133798 cites W1965668217 @default.
- W2076133798 cites W1967028169 @default.
- W2076133798 cites W1970959284 @default.
- W2076133798 cites W1972498490 @default.
- W2076133798 cites W1973626866 @default.
- W2076133798 cites W1974838631 @default.
- W2076133798 cites W1975226503 @default.
- W2076133798 cites W1975573364 @default.
- W2076133798 cites W1980316342 @default.
- W2076133798 cites W1981858986 @default.
- W2076133798 cites W1983226464 @default.
- W2076133798 cites W1983338834 @default.
- W2076133798 cites W1990777582 @default.
- W2076133798 cites W1991937784 @default.
- W2076133798 cites W1994609764 @default.
- W2076133798 cites W1995128285 @default.
- W2076133798 cites W1995792670 @default.
- W2076133798 cites W1995841143 @default.
- W2076133798 cites W2006712304 @default.
- W2076133798 cites W2009970530 @default.
- W2076133798 cites W2010160781 @default.
- W2076133798 cites W2012866556 @default.
- W2076133798 cites W2015745141 @default.
- W2076133798 cites W2016218486 @default.
- W2076133798 cites W2020317621 @default.
- W2076133798 cites W2021661590 @default.
- W2076133798 cites W2023271753 @default.
- W2076133798 cites W2028492701 @default.
- W2076133798 cites W2031969088 @default.
- W2076133798 cites W2032237190 @default.
- W2076133798 cites W2033666925 @default.
- W2076133798 cites W2035586701 @default.
- W2076133798 cites W2037459195 @default.
- W2076133798 cites W2038531399 @default.
- W2076133798 cites W2039354910 @default.
- W2076133798 cites W2041718798 @default.
- W2076133798 cites W2049526532 @default.
- W2076133798 cites W2057980421 @default.
- W2076133798 cites W2058210956 @default.
- W2076133798 cites W2058985876 @default.
- W2076133798 cites W2059096946 @default.
- W2076133798 cites W2059620799 @default.
- W2076133798 cites W2060814135 @default.
- W2076133798 cites W2063694470 @default.
- W2076133798 cites W2064558095 @default.
- W2076133798 cites W2070203126 @default.
- W2076133798 cites W2071379232 @default.
- W2076133798 cites W2082174377 @default.
- W2076133798 cites W2086957099 @default.
- W2076133798 cites W2087652483 @default.
- W2076133798 cites W2088913693 @default.
- W2076133798 cites W2090860050 @default.
- W2076133798 cites W2092210634 @default.
- W2076133798 cites W2110503115 @default.
- W2076133798 cites W2111502563 @default.
- W2076133798 cites W2116136214 @default.
- W2076133798 cites W2122619733 @default.
- W2076133798 cites W2127277619 @default.
- W2076133798 cites W2133477280 @default.
- W2076133798 cites W2140886907 @default.
- W2076133798 cites W2143785581 @default.
- W2076133798 cites W2145773666 @default.
- W2076133798 cites W2150098632 @default.
- W2076133798 cites W2155867968 @default.
- W2076133798 cites W2159963179 @default.
- W2076133798 cites W2167871252 @default.
- W2076133798 cites W2314822185 @default.
- W2076133798 cites W2321283660 @default.
- W2076133798 cites W2321972685 @default.
- W2076133798 cites W2325521290 @default.
- W2076133798 cites W2330290939 @default.
- W2076133798 cites W2332433683 @default.
- W2076133798 cites W2334956137 @default.
- W2076133798 cites W2335051141 @default.
- W2076133798 cites W2487292107 @default.
- W2076133798 cites W2949155689 @default.
- W2076133798 cites W2949304938 @default.
- W2076133798 cites W2950519944 @default.
- W2076133798 cites W2950929877 @default.
- W2076133798 cites W2951018975 @default.
- W2076133798 cites W2951174467 @default.
- W2076133798 cites W2951632152 @default.
- W2076133798 cites W2951844988 @default.
- W2076133798 cites W2951951611 @default.