Cabrero Antonino, JR.; Leyva Perez, A.; Corma Canós, A. (2012). Regioselective Hydration of Alkynes by Iron(III) Lewis/Brønsted Catalysis. Chemistry - A European Journal. 18(35):11107-11114. doi:10.1002/chem.201200580
Por favor, use este identificador para citar o enlazar este ítem: http://hdl.handle.net/10251/33630
Title:
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Regioselective Hydration of Alkynes by Iron(III) Lewis/Brønsted Catalysis
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Author:
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Cabrero Antonino, Jose Ramón
Leyva Perez, Antonio
Corma Canós, Avelino
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UPV Unit:
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Universitat Politècnica de València. Departamento de Química - Departament de Química
Universitat Politècnica de València. Instituto Universitario Mixto de Tecnología Química - Institut Universitari Mixt de Tecnologia Química
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Issued date:
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Abstract:
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The triflimide iron(III) salt [Fe(NTf2)3] promotes the direct hydration of terminal and internal alkynes with very good Markovnikov regioselectivities and high yields. The enhanced carbophilic Lewis acidity of the FeIII ...[+]
The triflimide iron(III) salt [Fe(NTf2)3] promotes the direct hydration of terminal and internal alkynes with very good Markovnikov regioselectivities and high yields. The enhanced carbophilic Lewis acidity of the FeIII cation mediated by the weakly-coordinating triflimide anion is crucial for the catalytic activity. The iron(III) metal salt can be recycled in the form of the OPPh3/[Fe(NTf2)3] system with similar activity and selectivity. However, spectroscopic and kinetic studies show that [Fe(NTf2)3] hydrolyzes under the reaction conditions and that catalytically less active Brønsted species are formed, which points to a Lewis/Brønsted co-catalysis. This triflimide-based catalytic system is regioselective for the hydration of internal aryl-alkynes and opens the door to a new synthetic route to alkyl ketophenones. As a proof of concept, the synthesis of two antipsychotics Haloperidol and Melperone, with general butyrophenone-like structure, is shown.
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Subjects:
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Alkynes
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Anions
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Ketones
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Regioselectivity
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Iron
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Hydration
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Copyrigths:
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Cerrado |
Source:
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Chemistry - A European Journal. (issn:
0947-6539
)
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DOI:
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10.1002/chem.201200580
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Publisher:
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Wiley-VCH Verlag
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Publisher version:
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http://dx.doi.org/10.1002/chem.201200580
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Thanks:
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The work has been supported by Consolider-Ingenio 2010 (proyecto MULTICAT), and PROMETEO from Generalitat Valenciana. J.R.C.A. thanks MCIINN for a pre-doctoral FPU fellowship. A. L. P. thanks ITQ for financial support. We ...[+]
The work has been supported by Consolider-Ingenio 2010 (proyecto MULTICAT), and PROMETEO from Generalitat Valenciana. J.R.C.A. thanks MCIINN for a pre-doctoral FPU fellowship. A. L. P. thanks ITQ for financial support. We thank Dr. J. A. Vidal-Moya for the EPR measurements.
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Type:
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Artículo
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