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Endohedral metal-induced regioselective formation of bis-prato adduct of Y3N@ Ih-C80 and Gd3N@ Ih-C80

Regioselective bisaddition of M3N@Ih-C80 (M = Y, Gd) was observed for the first time in the Prato reaction with N-ethylglycine and formaldehyde. The main kinetic bisadduct of Y3N@C80 was determined to be a [6,6],[6,6] adduct by 1H and 13C NMR and vis/NIR spectroscopy, and it converted to a mixture of regioisomers upon heating via a sigmatropic rearrangement. The main kinetic bisadduct of Gd3N@C80 (the [6,6],[6,6] adduct on the basis of vis/NIR data) existed stably under thermal conditions without isomerization. The likely position of the second addition of the Gd3N@C80 bisadduct was predicted by DFT calculation

This research was supported in part by the Swiss National Foundation (200021-140451 and 200021-156097 to Y.Y.), ETHZ (Grant ETH-25 11-1 to Y.Y.), JST PRESTO (to Y.Y.), the American Heart Association (SDG 0930140N to Y.Y.), the Spanish MECD (Ph.D. Fellowship AP2010-2517 to M.G.-B.), Spanish MINECO (Projects CTQ2011-23156/BQU and CTQ2011-25086/BQU and Juan de la Cierva Postdoctoral Grant JCI-2012-14438 to S.O.), and the European Community (CIG Project PCIG14-GA-2013-630978 to S.O.)

© Journal of the American Chemical Society, 2015, vol. 137, núm. 1, p. 58-61

American Chemical Society (ACS)

Autor: Aroua, Safwan
Garcia Borràs, Marc
Bölter, Marc Florian
Osuna Oliveras, Sílvia
Yamakoshi, Yoko
Data: 2015
Resum: Regioselective bisaddition of M3N@Ih-C80 (M = Y, Gd) was observed for the first time in the Prato reaction with N-ethylglycine and formaldehyde. The main kinetic bisadduct of Y3N@C80 was determined to be a [6,6],[6,6] adduct by 1H and 13C NMR and vis/NIR spectroscopy, and it converted to a mixture of regioisomers upon heating via a sigmatropic rearrangement. The main kinetic bisadduct of Gd3N@C80 (the [6,6],[6,6] adduct on the basis of vis/NIR data) existed stably under thermal conditions without isomerization. The likely position of the second addition of the Gd3N@C80 bisadduct was predicted by DFT calculation
This research was supported in part by the Swiss National Foundation (200021-140451 and 200021-156097 to Y.Y.), ETHZ (Grant ETH-25 11-1 to Y.Y.), JST PRESTO (to Y.Y.), the American Heart Association (SDG 0930140N to Y.Y.), the Spanish MECD (Ph.D. Fellowship AP2010-2517 to M.G.-B.), Spanish MINECO (Projects CTQ2011-23156/BQU and CTQ2011-25086/BQU and Juan de la Cierva Postdoctoral Grant JCI-2012-14438 to S.O.), and the European Community (CIG Project PCIG14-GA-2013-630978 to S.O.)
Format: application/pdf
ISSN: 0002-7863 (versió paper)
1520-5126 (versió electrònica)
Accés al document: http://hdl.handle.net/10256/10359
Llenguatge: eng
Editor: American Chemical Society (ACS)
Col·lecció: MICINN/PN 2012-2014/CTQ2011-23156
MICINN/PN 2012-2014/CTQ2011-25086
Reproducció digital del document publicat a: http://dx.doi.org/10.1021/ja511008z
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/630978
És part de: © Journal of the American Chemical Society, 2015, vol. 137, núm. 1, p. 58-61
Drets: Tots els drets reservats
Matèria: Reaccions químiques regioselectives
Regioselectivity Chemical reactions
Funcional de densitat, Teoria del
Density functionals
Títol: Endohedral metal-induced regioselective formation of bis-prato adduct of Y3N@ Ih-C80 and Gd3N@ Ih-C80
Tipus: info:eu-repo/semantics/article
Repositori: DUGiDocs

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