Počet záznamů: 1
Synthesis of highly polarized [3]dendralenes and their Diels-Alder reactions
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SYSNO ASEP 0576490 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název Synthesis of highly polarized [3]dendralenes and their Diels-Alder reactions Tvůrce(i) Antal, R. (CZ)
Staś, Monika (UOCHB-X) ORCID
Perdomo, S. M. (CZ)
Štemberová, M. (CZ)
Brůža, Z. (CZ)
Matouš, P. (CZ)
Kratochvíl, J. (CZ)
Růžička, A. (CZ)
Rulíšek, Lubomír (UOCHB-X) RID, ORCID
Kuneš, J. (CZ)
Kočovský, P. (CZ)
Andris, Erik (UOCHB-X) ORCID
Pour, M. (CZ)Zdroj.dok. Organic Chemistry Frontiers. - : Royal Society of Chemistry - ISSN 2052-4129
Roč. 10, č. 22 (2023), s. 5568-5578Poč.str. 11 s. Jazyk dok. eng - angličtina Země vyd. GB - Velká Británie Klíč. slova cross-coupling reactions ; dendralenes ; generation Obor OECD Physical chemistry Výzkumná infrastruktura e-INFRA CZ - 90140 - CESNET, zájmové sdružení právnických osob Způsob publikování Open access Institucionální podpora UOCHB-X - RVO:61388963 UT WOS 001067884500001 EID SCOPUS 85172865440 DOI 10.1039/D3QO01221B Anotace The diene-transmissive Diels-Alder (DTDA) reactions of dendralenes are emerging as a powerful synthetic tool. To date, these processes have been studied with non-polarized or mildly polarized species. We now present an expedient synthesis of strongly electron-deficient [3]dendralenes and demonstrate, for the first time, their DTDA reactions with electron-poor dienophiles. While the combination of two electron-poor partners is believed to be generally disfavored, DTDA reactions reported herein proceed at 100 & DEG,C with high yields and stereoselectivities. DFT calculations show that this electronically disfavored process is encouraged by a steric effect of the vinylic moiety within the dendralene core, driving the diene segment into the s-cis conformation, thereby lowering the activation energy by 2-3 kcal mol-1. While the free energy barrier is typically lower for the second cycloaddition, the two barriers become similar for dendralenes with a cyclic enone fragment, which allows a controlled stepwise addition of two different dienophiles. Pracoviště Ústav organické chemie a biochemie Kontakt asep@uochb.cas.cz ; Kateřina Šperková, Tel.: 232 002 584 ; Jana Procházková, Tel.: 220 183 418 Rok sběru 2024 Elektronická adresa https://doi.org/10.1039/D3QO01221B
Počet záznamů: 1