Matches in SemOpenAlex for { <https://semopenalex.org/work/W2926577592> ?p ?o ?g. }
- W2926577592 endingPage "7193" @default.
- W2926577592 startingPage "7181" @default.
- W2926577592 abstract "Controlling the regioselectivity of ambident nucleophiles toward alkylating agents is a fundamental problem in heterocyclic chemistry. Unsubstituted triazoles are particularly challenging, often requiring inefficient stepwise protection–deprotection strategies and prefunctionalization protocols. Herein we report on the alkylation of archetypal ambident 1,2,4-triazole, 1,2,3-triazole, and their anions, analyzed by in situ 1H/19F NMR, kinetic modeling, diffusion-ordered NMR spectroscopy, X-ray crystallography, highly correlated coupled-cluster computations [CCSD(T)-F12, DF-LCCSD(T)-F12, DLPNO-CCSD(T)], and Marcus theory. The resulting mechanistic insights allow design of an organocatalytic methodology for ambident control in the direct N-alkylation of unsubstituted triazole anions. Amidinium and guanidinium receptors are shown to act as strongly coordinating phase-transfer organocatalysts, shuttling triazolate anions into solution. The intimate ion pairs formed in solution retain the reactivity of liberated triazole anions but, by virtue of highly regioselective ion pairing, exhibit alkylation selectivities that are completely inverted (1,2,4-triazole) or substantially enhanced (1,2,3-triazole) compared to the parent anions. The methodology allows direct access to 4-alkyl-1,2,4-triazoles (rr up to 94:6) and 1-alkyl-1,2,3-triazoles (rr up to 99:1) in one step. Regioselective ion pairing acts in effect as a noncovalent in situ protection mechanism, a concept that may have broader application in the control of ambident systems." @default.
- W2926577592 created "2019-04-11" @default.
- W2926577592 creator A5004567326 @default.
- W2926577592 creator A5013677086 @default.
- W2926577592 creator A5038360767 @default.
- W2926577592 date "2019-04-04" @default.
- W2926577592 modified "2023-10-17" @default.
- W2926577592 title "Taming Ambident Triazole Anions: Regioselective Ion Pairing Catalyzes Direct N-Alkylation with Atypical Regioselectivity" @default.
- W2926577592 cites W1967458949 @default.
- W2926577592 cites W1968652549 @default.
- W2926577592 cites W1975024782 @default.
- W2926577592 cites W1983047899 @default.
- W2926577592 cites W1984735202 @default.
- W2926577592 cites W1990108100 @default.
- W2926577592 cites W1996044989 @default.
- W2926577592 cites W1999809919 @default.
- W2926577592 cites W2006365071 @default.
- W2926577592 cites W2015473274 @default.
- W2926577592 cites W2033451838 @default.
- W2926577592 cites W2038109973 @default.
- W2926577592 cites W2050218754 @default.
- W2926577592 cites W2057003691 @default.
- W2926577592 cites W2065501854 @default.
- W2926577592 cites W2069063040 @default.
- W2926577592 cites W2070230031 @default.
- W2926577592 cites W2077039514 @default.
- W2926577592 cites W2079050656 @default.
- W2926577592 cites W2086180379 @default.
- W2926577592 cites W2086312166 @default.
- W2926577592 cites W2090391132 @default.
- W2926577592 cites W2096123351 @default.
- W2926577592 cites W2118598169 @default.
- W2926577592 cites W2120730508 @default.
- W2926577592 cites W2125093214 @default.
- W2926577592 cites W2132611334 @default.
- W2926577592 cites W2137253163 @default.
- W2926577592 cites W2141079936 @default.
- W2926577592 cites W2144279905 @default.
- W2926577592 cites W2145662716 @default.
- W2926577592 cites W2146666644 @default.
- W2926577592 cites W2149200912 @default.
- W2926577592 cites W2159753333 @default.
- W2926577592 cites W2319608516 @default.
- W2926577592 cites W2320201800 @default.
- W2926577592 cites W2331404422 @default.
- W2926577592 cites W2774152116 @default.
- W2926577592 cites W2802961578 @default.
- W2926577592 cites W2899160630 @default.
- W2926577592 cites W2911570773 @default.
- W2926577592 cites W2949484111 @default.
- W2926577592 cites W2951082470 @default.
- W2926577592 cites W2951087633 @default.
- W2926577592 cites W2952150643 @default.
- W2926577592 cites W4247737473 @default.
- W2926577592 cites W4248552256 @default.
- W2926577592 cites W4256634851 @default.
- W2926577592 doi "https://doi.org/10.1021/jacs.9b02786" @default.
- W2926577592 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/30943722" @default.
- W2926577592 hasPublicationYear "2019" @default.
- W2926577592 type Work @default.
- W2926577592 sameAs 2926577592 @default.
- W2926577592 citedByCount "26" @default.
- W2926577592 countsByYear W29265775922019 @default.
- W2926577592 countsByYear W29265775922020 @default.
- W2926577592 countsByYear W29265775922021 @default.
- W2926577592 countsByYear W29265775922022 @default.
- W2926577592 countsByYear W29265775922023 @default.
- W2926577592 crossrefType "journal-article" @default.
- W2926577592 hasAuthorship W2926577592A5004567326 @default.
- W2926577592 hasAuthorship W2926577592A5013677086 @default.
- W2926577592 hasAuthorship W2926577592A5038360767 @default.
- W2926577592 hasBestOaLocation W29265775922 @default.
- W2926577592 hasConcept C112887158 @default.
- W2926577592 hasConcept C137277065 @default.
- W2926577592 hasConcept C142724271 @default.
- W2926577592 hasConcept C147597530 @default.
- W2926577592 hasConcept C155647269 @default.
- W2926577592 hasConcept C161790260 @default.
- W2926577592 hasConcept C164361826 @default.
- W2926577592 hasConcept C178790620 @default.
- W2926577592 hasConcept C178907741 @default.
- W2926577592 hasConcept C185592680 @default.
- W2926577592 hasConcept C204787440 @default.
- W2926577592 hasConcept C21951064 @default.
- W2926577592 hasConcept C2776910235 @default.
- W2926577592 hasConcept C2777907353 @default.
- W2926577592 hasConcept C2780020378 @default.
- W2926577592 hasConcept C2780263894 @default.
- W2926577592 hasConcept C32909587 @default.
- W2926577592 hasConcept C59759590 @default.
- W2926577592 hasConcept C66974803 @default.
- W2926577592 hasConcept C71240020 @default.
- W2926577592 hasConcept C71924100 @default.
- W2926577592 hasConceptScore W2926577592C112887158 @default.
- W2926577592 hasConceptScore W2926577592C137277065 @default.
- W2926577592 hasConceptScore W2926577592C142724271 @default.
- W2926577592 hasConceptScore W2926577592C147597530 @default.
- W2926577592 hasConceptScore W2926577592C155647269 @default.