Matches in SemOpenAlex for { <https://semopenalex.org/work/W2259599737> ?p ?o ?g. }
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- W2259599737 abstract "Pericyclic reactions bypass high-energy reactive intermediates by synchronizing bond formation and bond cleavage. The present work offers two strategies for uncoupling these two processes and converting concerted processes into their “interrupted” versions by combining Au(I) catalysis with electronic and stereoelectronic factors. First, we show how the alignment of the C3–C4 bond with the adjacent π systems can control the reactivity and how the concerted scission of the central σ bond is prevented in the boat conformation. Second, the introduction of a fluorine atom at C3 also interrupts the sigmatropic shift and changes the rate-determining step of the interrupted cascade from the 6-endo-dig nucleophilic attack to the fragmentation of the central C3–C4 bond. Furthermore, this effect strongly depends on the relative orientation of the C–F bond toward the developing cationic center. The equatorial C–F bond has a much greater destabilizing effect on TS2 due to the more efficient through-bond interaction between the acceptor and the cationic π system. In contrast, the axial C–F bond is not aligned with the bridging C–C bonds and does not impose an equally strong deactivating stereoelectronic effect. These differences illustrate that the competition between concerted and interrupted pericyclic pathways can be finely tuned via a combination of structural and electronic effects modulated by conformational equilibria. The combination of Au(I) catalysis and C–F-mediated stereoelectronic gating delays the central bond scission, opening access to the interrupted Cope rearrangements and expanding the scope of this classic reaction to the design of new cascade transformations." @default.
- W2259599737 created "2016-06-24" @default.
- W2259599737 creator A5041763415 @default.
- W2259599737 creator A5065292227 @default.
- W2259599737 creator A5082162394 @default.
- W2259599737 date "2016-02-23" @default.
- W2259599737 modified "2023-10-10" @default.
- W2259599737 title "Gold(I)-Catalyzed Allenyl Cope Rearrangement: Evolution from Asynchronicity to Trappable Intermediates Assisted by Stereoelectronic Switching" @default.
- W2259599737 cites W1159484598 @default.
- W2259599737 cites W1934560651 @default.
- W2259599737 cites W1943239313 @default.
- W2259599737 cites W1964587503 @default.
- W2259599737 cites W1964801890 @default.
- W2259599737 cites W1966878394 @default.
- W2259599737 cites W1968833030 @default.
- W2259599737 cites W1969374702 @default.
- W2259599737 cites W1969385751 @default.
- W2259599737 cites W1974533319 @default.
- W2259599737 cites W1974642566 @default.
- W2259599737 cites W1975134422 @default.
- W2259599737 cites W1975755749 @default.
- W2259599737 cites W1977979911 @default.
- W2259599737 cites W1979651460 @default.
- W2259599737 cites W1980796942 @default.
- W2259599737 cites W1981805424 @default.
- W2259599737 cites W1984990773 @default.
- W2259599737 cites W1986686065 @default.
- W2259599737 cites W1987578126 @default.
- W2259599737 cites W1988734990 @default.
- W2259599737 cites W1988872630 @default.
- W2259599737 cites W1989193352 @default.
- W2259599737 cites W1989212194 @default.
- W2259599737 cites W1990396358 @default.
- W2259599737 cites W1994041628 @default.
- W2259599737 cites W1994080929 @default.
- W2259599737 cites W1997504607 @default.
- W2259599737 cites W1998375603 @default.
- W2259599737 cites W1998573948 @default.
- W2259599737 cites W1999081447 @default.
- W2259599737 cites W2000099719 @default.
- W2259599737 cites W2001366978 @default.
- W2259599737 cites W2001693653 @default.
- W2259599737 cites W2004226047 @default.
- W2259599737 cites W2004362149 @default.
- W2259599737 cites W2009066290 @default.
- W2259599737 cites W2009445872 @default.
- W2259599737 cites W2009610562 @default.
- W2259599737 cites W2009703228 @default.
- W2259599737 cites W2011077346 @default.
- W2259599737 cites W2011153362 @default.
- W2259599737 cites W2014377908 @default.
- W2259599737 cites W2016845143 @default.
- W2259599737 cites W2019567419 @default.
- W2259599737 cites W2021811173 @default.
- W2259599737 cites W2024168171 @default.
- W2259599737 cites W2025495088 @default.
- W2259599737 cites W2031302171 @default.
- W2259599737 cites W2033972881 @default.
- W2259599737 cites W2034666141 @default.
- W2259599737 cites W2034903872 @default.
- W2259599737 cites W2037461964 @default.
- W2259599737 cites W2038767330 @default.
- W2259599737 cites W2038834383 @default.
- W2259599737 cites W2039126203 @default.
- W2259599737 cites W2040702384 @default.
- W2259599737 cites W2040860735 @default.
- W2259599737 cites W2046260505 @default.
- W2259599737 cites W2047047972 @default.
- W2259599737 cites W2048058979 @default.
- W2259599737 cites W2048451151 @default.
- W2259599737 cites W2050462119 @default.
- W2259599737 cites W2052043507 @default.
- W2259599737 cites W2052649855 @default.
- W2259599737 cites W2053270747 @default.
- W2259599737 cites W2053721765 @default.
- W2259599737 cites W2054281584 @default.
- W2259599737 cites W2055961800 @default.
- W2259599737 cites W2060527124 @default.
- W2259599737 cites W2062778326 @default.
- W2259599737 cites W2066352529 @default.
- W2259599737 cites W2066539787 @default.
- W2259599737 cites W2074548211 @default.
- W2259599737 cites W2074939609 @default.
- W2259599737 cites W2075980246 @default.
- W2259599737 cites W2085739350 @default.
- W2259599737 cites W2087931197 @default.
- W2259599737 cites W2088159007 @default.
- W2259599737 cites W2088209473 @default.
- W2259599737 cites W2088808945 @default.
- W2259599737 cites W2089771537 @default.
- W2259599737 cites W2089777445 @default.
- W2259599737 cites W2090004279 @default.
- W2259599737 cites W2090664260 @default.
- W2259599737 cites W2091727457 @default.
- W2259599737 cites W2092340089 @default.
- W2259599737 cites W2093473385 @default.
- W2259599737 cites W2093509922 @default.
- W2259599737 cites W2094065247 @default.