Matches in SemOpenAlex for { <https://semopenalex.org/work/W2784427457> ?p ?o ?g. }
- W2784427457 endingPage "249" @default.
- W2784427457 startingPage "249" @default.
- W2784427457 abstract "The Mallory (photocyclization) and Scholl (thermal cyclohydrogenation) reactions are widely used in the synthesis of extended conjugated π systems of high scientific interest and technological importance, including molecular wires, semiconducting polymers, and nanographenes. While simple electrocyclization reactions obey the Woodward-Hoffman rules, no such simple, general, and powerful model is available for eliminative cyclization reactions due to their increased mechanistic complexity. In this work, detailed mechanistic investigations of prototypical reactions reveal that there is no single rate-determining step for thermal oxidative dehydrogenation reactions, but they are very sensitive to the presence and distribution of heteroatoms around the photocyclizing ring system. Key aspects of reactivity are correlated to the constituent ring oxidation potentials. For photocyclization reactions, planarization occurs readily and/or spontaneously following photo-excitation, and is promoted by heteroatoms within 5-membered ring adjacent to the photocyclizing site. Oxidative photocyclization requires intersystem crossing to proceed to products, while reactants configured to undergo purely eliminative photocyclization could proceed to products entirely in the excited state. Overall, oxidative photocyclization seems to strike the optimal balance between synthetic convenience (ease of preparation of reactants, mild conditions, tolerant to chemical diversity in reactants) and favourable kinetic and thermodynamic properties." @default.
- W2784427457 created "2018-02-02" @default.
- W2784427457 creator A5075970032 @default.
- W2784427457 creator A5076423650 @default.
- W2784427457 date "2018-01-01" @default.
- W2784427457 modified "2023-09-25" @default.
- W2784427457 title "Beyond the Woodward-Hoffman Rules: What Controls Reactivity in Eliminative Aromatic Ring-Forming Reactions?" @default.
- W2784427457 cites W1597956323 @default.
- W2784427457 cites W1601262259 @default.
- W2784427457 cites W1621741947 @default.
- W2784427457 cites W1970241538 @default.
- W2784427457 cites W1971133570 @default.
- W2784427457 cites W1973336827 @default.
- W2784427457 cites W1982151759 @default.
- W2784427457 cites W1982356449 @default.
- W2784427457 cites W1990835465 @default.
- W2784427457 cites W1992288430 @default.
- W2784427457 cites W2008517988 @default.
- W2784427457 cites W2008844584 @default.
- W2784427457 cites W2012961504 @default.
- W2784427457 cites W2014935324 @default.
- W2784427457 cites W2016392672 @default.
- W2784427457 cites W2023433398 @default.
- W2784427457 cites W2026172453 @default.
- W2784427457 cites W2030975645 @default.
- W2784427457 cites W2031596719 @default.
- W2784427457 cites W2033990154 @default.
- W2784427457 cites W2039568596 @default.
- W2784427457 cites W2040994768 @default.
- W2784427457 cites W2041932124 @default.
- W2784427457 cites W2042806090 @default.
- W2784427457 cites W2044606025 @default.
- W2784427457 cites W2046412723 @default.
- W2784427457 cites W2046925216 @default.
- W2784427457 cites W2048634728 @default.
- W2784427457 cites W2048910222 @default.
- W2784427457 cites W2049996223 @default.
- W2784427457 cites W2052564088 @default.
- W2784427457 cites W2058129958 @default.
- W2784427457 cites W2058848030 @default.
- W2784427457 cites W2058957873 @default.
- W2784427457 cites W2060080789 @default.
- W2784427457 cites W2061709283 @default.
- W2784427457 cites W2062638006 @default.
- W2784427457 cites W2068283517 @default.
- W2784427457 cites W2068617439 @default.
- W2784427457 cites W2072215160 @default.
- W2784427457 cites W2075151864 @default.
- W2784427457 cites W2080449510 @default.
- W2784427457 cites W2082797262 @default.
- W2784427457 cites W2086673865 @default.
- W2784427457 cites W2086841419 @default.
- W2784427457 cites W2087999652 @default.
- W2784427457 cites W2088959145 @default.
- W2784427457 cites W2090829971 @default.
- W2784427457 cites W2092057169 @default.
- W2784427457 cites W2094397888 @default.
- W2784427457 cites W2095563975 @default.
- W2784427457 cites W2095706086 @default.
- W2784427457 cites W2098805136 @default.
- W2784427457 cites W2098963943 @default.
- W2784427457 cites W2099629334 @default.
- W2784427457 cites W2101078794 @default.
- W2784427457 cites W2103785650 @default.
- W2784427457 cites W2111343751 @default.
- W2784427457 cites W2130029082 @default.
- W2784427457 cites W2138196788 @default.
- W2784427457 cites W2141844037 @default.
- W2784427457 cites W2150921488 @default.
- W2784427457 cites W2153662628 @default.
- W2784427457 cites W2155273994 @default.
- W2784427457 cites W2170387452 @default.
- W2784427457 cites W2316808493 @default.
- W2784427457 cites W2318468106 @default.
- W2784427457 cites W2320823423 @default.
- W2784427457 cites W2323511279 @default.
- W2784427457 cites W2329180391 @default.
- W2784427457 cites W2333678836 @default.
- W2784427457 cites W2344627999 @default.
- W2784427457 cites W2736710089 @default.
- W2784427457 cites W2938000732 @default.
- W2784427457 cites W71509095 @default.
- W2784427457 cites W1968525451 @default.
- W2784427457 doi "https://doi.org/10.1071/ch17564" @default.
- W2784427457 hasPublicationYear "2018" @default.
- W2784427457 type Work @default.
- W2784427457 sameAs 2784427457 @default.
- W2784427457 citedByCount "2" @default.
- W2784427457 countsByYear W27844274572019 @default.
- W2784427457 countsByYear W27844274572021 @default.
- W2784427457 crossrefType "journal-article" @default.
- W2784427457 hasAuthorship W2784427457A5075970032 @default.
- W2784427457 hasAuthorship W2784427457A5076423650 @default.
- W2784427457 hasBestOaLocation W27844274572 @default.
- W2784427457 hasConcept C119889771 @default.
- W2784427457 hasConcept C121332964 @default.
- W2784427457 hasConcept C142724271 @default.
- W2784427457 hasConcept C147597530 @default.