Silyloxyazadienes: one intermediate and two competitive pericyclic reactions (Articolo in rivista)

Type

• Articolo in rivista (Classe)
• Prodotto della ricerca (Classe)

Label

• Silyloxyazadienes: one intermediate and two competitive pericyclic reactions (Articolo in rivista) (literal)

Anno

• 2010-01-01T00:00:00+01:00 (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi

• 10.1039/b925351c (literal)

Alternative label

• VENTURINI, ALESSANDRO (1); Panunzio, Mauro (1); Bongini, Alessandro (2) (2010)
  Silyloxyazadienes: one intermediate and two competitive pericyclic reactions
  in PCCP. Physical chemistry chemical physics (Print)
  (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori

• VENTURINI, ALESSANDRO (1); Panunzio, Mauro (1); Bongini, Alessandro (2) (literal)

Pagina inizio

• 5067 (literal)

Pagina fine

• 5073 (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume

• 12 (literal)

Rivista

• PCCP. Physical chemistry chemical physics (Rivista)

Note

• ISI Web of Science (WOS) (literal)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni

• 1) Department of Chemistry G. Ciamician - ; (2) Institute for the Organic Synthesis and Photoreactivity - National Research Council of Italy (literal)

Titolo

• Silyloxyazadienes: one intermediate and two competitive pericyclic reactions (literal)

Abstract

• The two competing mechanisms in the reaction of 3-trialkylsilyloxy-2-aza-1,3 dienes to form b-lactams through a [2+2] electrocyclic ring closure or tetrahydrooxazin-2-ones via a [4+2] hetero Diels-Alder reaction were studied using Density Functional computations. Although the [2+2] and [4+2] mechanisms are typical of dienes, their competition, starting from the same diene intermediate, has not yet been observed and analyzed. This competition is governed by a delicate interplay between temperature and substituents at the diene and dienophile respectively. Clearly, entropy tends to favor the [4+2] hetero Diels-Alder at low temperatures and the [2+2] electrocyclic ring closure at high temperatures, but a simple substituent modification at the diene and dienophile, can make the [4+2] competitive at high temperatures and sometimes even trasform the [4+2] concerted mechanism into a two-step Mukaiyama-type process. Moreover a study of the global electrophilicity values showed that charge transfer in the hetero Diels-Alder transition states is driven by chemical hardness rather than by chemical potential (literal)

Prodotto di

• MAteriali Funzionali Organici per applicazioni High-Tech: sistemi molecolari, supramolecolari e bioibridi (MAFO-HT) (PM.P04.003.003) (Modulo)
• Sintesi e caratterizzazione mediante metodologie chimiche innovative, di scaffold molecolari per l'individuazione di nuove molecole biologicamente attive. (PM.P03.011.002) (Modulo)
• Institute for organic syntheses and photoreactivity (ISOF) (Istituto)

Autore CNR

• ALESSANDRO VENTURINI (Persona)
• MAURO PANUNZIO (Persona)

Incoming links:

Prodotto

• Institute for organic syntheses and photoreactivity (ISOF) (Istituto)
• Sintesi e caratterizzazione mediante metodologie chimiche innovative, di scaffold molecolari per l'individuazione di nuove molecole biologicamente attive. (PM.P03.011.002) (Modulo)
• MAteriali Funzionali Organici per applicazioni High-Tech: sistemi molecolari, supramolecolari e bioibridi (MAFO-HT) (PM.P04.003.003) (Modulo)

Autore CNR di

• ALESSANDRO VENTURINI (Persona)
• MAURO PANUNZIO (Persona)

Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#rivistaDi

• PCCP. Physical chemistry chemical physics (Rivista)