Reaction profiling of visible-light-mediated [2 + 1] dearomatization vs. alkylation of electron-rich arenes with aryldiazoacetates: real-time NMR monitoring, kinetics, and computational analysis

Petrić, Karlo; Čikoš, Ana; Nikšić-Franjić, Ivana; Lloyd-Jones, Guy C.; Gredičak, Matija; Topolovčan, Nikola (2026) Reaction profiling of visible-light-mediated [2 + 1] dearomatization vs. alkylation of electron-rich arenes with aryldiazoacetates: real-time NMR monitoring, kinetics, and computational analysis. Organic Chemistry Frontiers, 13 (9). pp. 2794-2804. ISSN 2052-4129

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Abstract

An in-depth mechanistic and kinetic analysis of the dearomative [2 + 1] reaction between electron-rich arenes and aryldiazoesters for the regioselective and diastereoselective synthesis of norcaradienes is reported. Profiling the reaction through LED-NMR analysis gave kinetic insights into product formation and unwanted side reactions, and the influence of the electron-density profile on cyclopropanation vs. alkylation in the key dearomative step is elucidated by theoretical analysis. Synthetic utility of the obtained meso-norcaradienes was evaluated through their desymmetrization into products with six contiguous stereogenic centres, while reactive functional groups allow for subsequent manipulation into more complex carbocycles.

Item Type:	Article
Uncontrolled Keywords:	dearomatization; electron density; arene functionalization; LED-NMR; DFT
Subjects:	NATURAL SCIENCES > Chemistry > Organic Chemistry
Divisions:	Division of Organic Chemistry and Biochemistry NMR Center
Projects:	Project title Project leader Project code Project type Organokatalitičke dearomatizacijske strategije inspirirane prirodnim spojevima Matija Gredičak IP-2022-10-5184 HRZZ
Depositing User:	Ivana Vuglec
Date Deposited:	01 Sep 2026 12:28
URI:	https://fulir.irb.hr:/id/eprint/12132
DOI:	10.1039/d6qo00072j

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