Inverting the diastereoselectivity of the mukaiyama-michael addition with graphite-based catalysts

Handle URI:
http://hdl.handle.net/10754/563388
Title:
Inverting the diastereoselectivity of the mukaiyama-michael addition with graphite-based catalysts
Authors:
Acocella, Maria Rosaria; Mauro, Marco; Falivene, Laura; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Guerra, Gaetano
Abstract:
Here, we show that graphite-based catalysts, mainly graphite oxide (GO) and exfoliated GO, are effective recyclable catalysts for a relevant stereoselective Mukaiyama-Michael addition, outperforming currently available catalysts. Moreover, the graphite-based catalysts described here invert the diastereoselectivity relative to that observed with known catalysts, with the unprecedented large prevalence of the anti diastereoisomer. This inverted diastereoselectivity is increased when the catalyst concentration is reduced and after catalyst recycling. Density functional theory calculations suggest that the selectivity is determined by two types of supramolecular interactions operating between the catalyst and the substrates at the diastereoselectivity- determining transition state, specifically, the π-stacking of b-nitrostyrene with graphite and the van der Waals interaction between the SiMe3 group of the silyl ether and the graphite. © 2013 American Chemical Society.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program
Publisher:
American Chemical Society (ACS)
Journal:
ACS Catalysis
Issue Date:
7-Feb-2014
DOI:
10.1021/cs401053t
Type:
Article
ISSN:
21555435
Sponsors:
We thank Prof. Arrigo Scettri, Dr. Marialuigia Raimondo, and Prof. Liberata Guadagno for useful discussions. The Ministero dell' Istruzione dell' Universita e della Ricerca is gratefully acknowledged for financial support (PRIN).
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorAcocella, Maria Rosariaen
dc.contributor.authorMauro, Marcoen
dc.contributor.authorFalivene, Lauraen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorGuerra, Gaetanoen
dc.date.accessioned2015-08-03T11:47:19Zen
dc.date.available2015-08-03T11:47:19Zen
dc.date.issued2014-02-07en
dc.identifier.issn21555435en
dc.identifier.doi10.1021/cs401053ten
dc.identifier.urihttp://hdl.handle.net/10754/563388en
dc.description.abstractHere, we show that graphite-based catalysts, mainly graphite oxide (GO) and exfoliated GO, are effective recyclable catalysts for a relevant stereoselective Mukaiyama-Michael addition, outperforming currently available catalysts. Moreover, the graphite-based catalysts described here invert the diastereoselectivity relative to that observed with known catalysts, with the unprecedented large prevalence of the anti diastereoisomer. This inverted diastereoselectivity is increased when the catalyst concentration is reduced and after catalyst recycling. Density functional theory calculations suggest that the selectivity is determined by two types of supramolecular interactions operating between the catalyst and the substrates at the diastereoselectivity- determining transition state, specifically, the π-stacking of b-nitrostyrene with graphite and the van der Waals interaction between the SiMe3 group of the silyl ether and the graphite. © 2013 American Chemical Society.en
dc.description.sponsorshipWe thank Prof. Arrigo Scettri, Dr. Marialuigia Raimondo, and Prof. Liberata Guadagno for useful discussions. The Ministero dell' Istruzione dell' Universita e della Ricerca is gratefully acknowledged for financial support (PRIN).en
dc.publisherAmerican Chemical Society (ACS)en
dc.subjectcarbocatalysisen
dc.subjectgraphite-based catalystsen
dc.subjectinversion of diastereoselectivityen
dc.subjectMukaiyama-Michael additionen
dc.subjectsolvent-freeen
dc.titleInverting the diastereoselectivity of the mukaiyama-michael addition with graphite-based catalystsen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.identifier.journalACS Catalysisen
dc.contributor.institutionDepartment of Chemistry and Biology, INSTM Research Unit, Università di Salerno, via Giovanni Paolo II, 84084 Fisciano, Italyen
kaust.authorCavallo, Luigien
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.