Dimerizing cascades of enallenamides reveal the visible-light-promoted activation of cumulated C-C double bonds.

Autor:	Serafino A; Department of Chemistry, Life Sciences and Environmental Sustainability, Università di Parma Parco Area Delle Scienze 17/A 43124 Parma Italy giovanni.maestri@unipr.it., Chiminelli M; Department of Chemistry, Life Sciences and Environmental Sustainability, Università di Parma Parco Area Delle Scienze 17/A 43124 Parma Italy giovanni.maestri@unipr.it., Balestri D; Department of Chemistry, Life Sciences and Environmental Sustainability, Università di Parma Parco Area Delle Scienze 17/A 43124 Parma Italy giovanni.maestri@unipr.it., Marchiò L; Department of Chemistry, Life Sciences and Environmental Sustainability, Università di Parma Parco Area Delle Scienze 17/A 43124 Parma Italy giovanni.maestri@unipr.it., Bigi F; Department of Chemistry, Life Sciences and Environmental Sustainability, Università di Parma Parco Area Delle Scienze 17/A 43124 Parma Italy giovanni.maestri@unipr.it.; IMEM-CNR Parco Area Delle Scienze 37/A 43124 Parma Italy., Maggi RM; Department of Chemistry, Life Sciences and Environmental Sustainability, Università di Parma Parco Area Delle Scienze 17/A 43124 Parma Italy giovanni.maestri@unipr.it., Malacria M; Sorbonne Université, Faculty of Science and Engineering, IPCM (UMR CNRS 8232) 4 Place Jussieu 75252 Paris Cedex 05 France., Maestri G; Department of Chemistry, Life Sciences and Environmental Sustainability, Università di Parma Parco Area Delle Scienze 17/A 43124 Parma Italy giovanni.maestri@unipr.it.
Jazyk:	angličtina
Zdroj:	Chemical science [Chem Sci] 2022 Jan 26; Vol. 13 (9), pp. 2632-2639. Date of Electronic Publication: 2022 Jan 26 (Print Publication: 2022).
DOI:	10.1039/d1sc06719b
Abstrakt:	The visible-light-promoted activation of conjugated C-C double bonds is well developed, while that of cumulated systems is underexplored. We present the feasibility of this challenging approach. The localization of a triplet on an allenamide arm can be favored over that on a conjugated alkene. Allenamides with an arylacryloyl arm dimerize at room temperature in the presence of visible light and an iridium(iii) photocatalyst. Two orthogonal polycyclizations took place and their outcome is entirely dictated by the substitution of the alkene partner. Both cascades afford complex molecular architectures with high selectivity. Products form through the ordered rearrangement of twelve π electrons, providing a [3.2.0] bicyclic unit tethered to a fused tricycle, whose formation included an aryl C-H functionalization step, using disubstituted alkenes. The outcome was reverted with trisubstituted ones, which gave rise to taxane-like bridged tricycles that had two six-membered lactams flanking a cyclooctane ring, which was established through the creation of four alternate C-C bonds. Competing Interests: There are no conflicts to declare. (This journal is © The Royal Society of Chemistry.)
Databáze:	MEDLINE
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