Annulative p-extension of BODIPYs made easy via gold(I)-catalyzed cycloisomerization
Entity
UAM. Departamento de Química OrgánicaPublisher
Royal Society of ChemistryDate
2020-06-08Citation
10.1039/d0sc01054e
Chemical Science 11.39 (2020): 10778-10785
ISSN
2041-6520 (print); 2041-6539 (online)DOI
10.1039/d0sc01054eFunded by
Financial support from Spanish MINECO (CTQ2017-85393-P) is acknowledged. IMDEA Nanociencia acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, Grant SEV-2016-0686). J. L. acknowledges MECD, Spain, for a F.P.U. fellowship. The European Commission under the Marie Sklodowska-Curie Action Cofund 2015 (EU project 713366-InterTalentum) is acknowledged for the support for G.D.S. Generous allocation of computational time from the Centro de Computación Científica UAM is gratefully acknowledgedProject
Gobierno de España. CTQ2017-85393-P; Gobierno de España. SEV-2016-0686; info:eu-repo/grantAgreement/EC/H2020/713366/EU//InterTalentumEditor's Version
https://doi.org/10.1039/d0sc01054eSubjects
BODIPYs; Cycloisomerization; QuímicaRights
© 2020 The Royal Society of ChemistryAbstract
Here we report gold(i)-catalyzed cycloisomerization as a new powerful synthetic tool for the preparation of π-extended BODIPY derivatives. The catalytic system PPhF3AuCl/AgSbF6 enables the synthesis of [b]-[2,1]naphtho-fused-BODIPYs (2a-2c) under mild conditions, in excellent yields and short reaction times. The reaction is totally regioselective to the 6-endo-dig product and for the α-position of the BODIPY, which is both the kinetically and thermodynamically favored pathway, as supported by the free energy profile calculated by means of Density Functional Theory (DFT). Moreover, this methodology also allows the synthesis of two new families of [b]-aryl-fused-BODIPYs, namely, [3,4]phenanthro- (2e and 2f) and [1,2]naphtho-fused (2g) BODIPYs. Their molecular and electronic structures were established by NMR and UV-vis spectroscopies as well as single-crystal X-ray diffraction analysis. As can be noted from the X-ray structures, 2a, 2e and 2g present interesting structural differences at both the molecular and packing level. Interestingly, despite being isomers, the UV/vis spectra of 2a and 2g revealed significant differences in their electronic structures. The origin of this finding was studied by Time-Dependent DFT calculations. Calculated DFT Nuclear Independent Chemical Shift (NICS(0)) values also supported the different electronic structures of 2a and 2g
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Google Scholar:Labella, Jorge
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Durán Sampedro, Gonzalo
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Martínez Díaz, Victoria
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Torres Cebada, Tomás
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