When cobalt-mediated [2 + 2 + 2] cycloaddition reaction dares go astray: synthesis of unprecedented cobalt( iii )-complexes
| العنوان: | When cobalt-mediated [2 + 2 + 2] cycloaddition reaction dares go astray: synthesis of unprecedented cobalt( iii )-complexes |
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| المؤلفون: | Corinne Aubert, Marion Delorme, Paola Nava, Alexander Punter, Muriel Amatore, Laurent Commeiras, Raquel Oliveira, Yannick Carissan, Jean-Luc Parrain |
| المساهمون: | Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Processus d'Activation Sélective par Transfert d'Energie Uni-électronique ou Radiatif (UMR 8640) (PASTEUR), Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS) |
| المصدر: | Dalton Transactions Dalton Transactions, Royal Society of Chemistry, 2019, 48 (42), pp.15767-15771. ⟨10.1039/C9DT03311D⟩ Dalton Transactions, 2019, 48 (42), pp.15767-15771. ⟨10.1039/C9DT03311D⟩ |
| بيانات النشر: | HAL CCSD, 2019. |
| سنة النشر: | 2019 |
| مصطلحات موضوعية: | 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, chemistry.chemical_element, Mots Clefs Cycloaddition, Cobalt, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, butenolide, Cycloaddition, 0104 chemical sciences, Inorganic Chemistry, Fragmentation (mass spectrometry), chemistry, Moiety, Ene reaction, complex, Butenolide |
| الوصف: | International audience; In sharp contrast with the standard [2 + 2 + 2] cycloaddition reaction of diyne/ene, cobalt-mediated cycloadditions with γ-alkylidenebutenolide led to unprecedented cobalt(III) polycyclic complexes. A plausible mechanism supported by a computational study based on an unusual fragmentation of the butenolide moiety was postulated to account for this original reaction. The transition metal-catalyzed [2 + 2 + 2] cycloaddition reaction is well established as one of the most elegant methods for the rapid construction of functionalised aromatic and hetero-aromatic polycyclic compounds, as well as 1,3-cyclohexadiene derivatives. Since the original report of a metal-mediated [2 + 2 + 2] cycloaddition reaction of acetylene derivatives, 1 many groups have demonstrated the significance of this reaction through the use of various transition metal complexes, mainly from group 8-10 elements (Ir, Ru, Ni, Fe, Co, Rh, Nb the most employed). 2 Among all the available catalysts, CpCoL 2 complexes (L = CO, PR 3 , alkenes) have been frequently employed as an active source of "CpCo". Such systems have proved their efficiency (i) for the co-cyclisation of alkynes with alkenes to give cyclohexadiene products 1 in their complexed form, 2a (ii) for the linear 2 : 1 co-oligomerisation 3 of alkynes with acyclic enol ethers (R 3 = alkoxyl) to give 1-alkoxy-1,3,5-triene derivatives 2 (Scheme 1a). It is worth noting that the use of cyclic enol ethers such as 2,3-dihydrofuran produced unconju-gated 1,3,6-trienes 3 whereas benzofuran derivatives led to the formation of the corresponding CpCo-complexed cyclohexa-dienes. 4 Herein, we report the development of a cobalt-mediated polycyclisation reaction with the original enediynes 3 bearing an alkylidenebutenolide moiety. Compared to "classic" alkenes as well as "classic" enol ethers, alkylidene-butenolides display a unique exo-cyclic double bond. This double bond, which was never been used as 2π partner in intra-or intermolecular [2 + 2 + 2] cycloaddition reactions, could have two distinct electronic properties due to the cyclic enol acetate and γ,δ-unsaturated lactone moieties. This speci-ficity would account for the unusual reactivity (Scheme 1b and c). The main features of the present work include (i) formal (2 + 2 + 3) cycloaddition reaction, (ii) unprecedented formation of cobalt(III) complexes 4 featuring both π-allyl and carbanion ligands (highlighted in green in Scheme 1c) and (iii) high levels of regio-and diastereoselectivities. These cobalt(III) complexes rearranged in acidic conditions to give bicyclo[3.3.1] non-3-en-2-one scaffolds found in polyprenylated acylphloro-glucinol natural products. Furthermore, a mechanism pathway, supported by a computational approach, based on Scheme 1 Outcomes of cobalt(I)-mediated process. † Electronic supplementary information (ESI) available: Synthesis procedures, 1 H and 13 C NMR spectra of each compounds and computational studies. CCDC 1853760, 1853762, 1853766 and 1853778. For ESI and crystallographic data in CIF or other electronic format see |
| اللغة: | English |
| تدمد: | 1477-9226 1477-9234 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::0dafbc81240fdc41dc46433be9e0c8ef https://hal.archives-ouvertes.fr/hal-02354762/document |
| حقوق: | OPEN |
| رقم الأكسشن: | edsair.doi.dedup.....0dafbc81240fdc41dc46433be9e0c8ef |
| قاعدة البيانات: | OpenAIRE |
| تدمد: | 14779226 14779234 |
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