The photochemical reaction between some alkenyl boronates and benzophenone is described. While a pinacol alkenyl boronate derivative gave the corresponding oxetane, the MIDA esters gave a tertiary alcohol derived from allylic hydrogen abstraction by triplet benzophenone and coupling of the radicals thus obtained. A theoretical work at DFT level of theory performed on a MIDA ester explained this behaviour showing that the formation of the tertiary alcohol is the most probable reaction. Furthermore, the theoretical calculations showed that the PaternoeB€uchi reaction occurs giving the C,C biradical intermediate and this result is not in agreement with the previous described hypothesis where electron poor alkenes gave mainly the C,O biradical intermediate.

Paternó-Büchi reaction versus hydrogen abstraction in the photochemical reactivity of alkenyl boronates with benzophenone / A., D’Annibale; M., D’Auria; Prati, Fabio; Romagnoli, Chiara; S., Stoia; R., Racioppi; L., Viggiani. - In: TETRAHEDRON. - ISSN 0040-4020. - STAMPA. - 69:(2013), pp. 3782-3795. [10.1016/j.tet.2013.03.068]

Paternó-Büchi reaction versus hydrogen abstraction in the photochemical reactivity of alkenyl boronates with benzophenone

PRATI, Fabio;ROMAGNOLI, Chiara;
2013

Abstract

The photochemical reaction between some alkenyl boronates and benzophenone is described. While a pinacol alkenyl boronate derivative gave the corresponding oxetane, the MIDA esters gave a tertiary alcohol derived from allylic hydrogen abstraction by triplet benzophenone and coupling of the radicals thus obtained. A theoretical work at DFT level of theory performed on a MIDA ester explained this behaviour showing that the formation of the tertiary alcohol is the most probable reaction. Furthermore, the theoretical calculations showed that the PaternoeB€uchi reaction occurs giving the C,C biradical intermediate and this result is not in agreement with the previous described hypothesis where electron poor alkenes gave mainly the C,O biradical intermediate.
69
3782
3795
Paternó-Büchi reaction versus hydrogen abstraction in the photochemical reactivity of alkenyl boronates with benzophenone / A., D’Annibale; M., D’Auria; Prati, Fabio; Romagnoli, Chiara; S., Stoia; R., Racioppi; L., Viggiani. - In: TETRAHEDRON. - ISSN 0040-4020. - STAMPA. - 69:(2013), pp. 3782-3795. [10.1016/j.tet.2013.03.068]
A., D’Annibale; M., D’Auria; Prati, Fabio; Romagnoli, Chiara; S., Stoia; R., Racioppi; L., Viggiani
File in questo prodotto:
File Dimensione Formato  
Tetrahedron_2013_D'Auria.pdf

non disponibili

Tipologia: Post-print dell'autore (bozza post referaggio)
Dimensione 2.05 MB
Formato Adobe PDF
2.05 MB Adobe PDF   Visualizza/Apri   Richiedi una copia
Pubblicazioni consigliate

Caricamento pubblicazioni consigliate

Licenza Creative Commons
I metadati presenti in IRIS UNIMORE sono rilasciati con licenza Creative Commons CC0 1.0 Universal, mentre i file delle pubblicazioni sono rilasciati con licenza Attribuzione 4.0 Internazionale (CC BY 4.0), salvo diversa indicazione.
In caso di violazione di copyright, contattare Supporto Iris

Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11380/937889
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 7
  • ???jsp.display-item.citation.isi??? 8
social impact