Dichloroindium hydride revealed to be a valid alternative to tributyltin hydride for radical
reduction of organic (alkyl, aryl, acyl, solfonyl) azides. The new approach entails mild reaction
conditions and provides high yields of the corresponding amines and amides, also showing high
degrees of selectivity. The system dichloroindium hydride / azides can be utilised in fivemembered
ring closures of g-azidonitriles, as a new source of aminyl radicals for the attractive
synthesis of interesting amidine compounds in the absence of both toxic reagents and tedious
purification procedures. Allylindium dichloride seems a good substitute for dichloroindium
hydride for generation of indium centred radicals under photolytic conditions, since it allows
allylation of electrophilic azides (e.g. phenylsulfonyl azide) and halogen or ester δ-substituted
azides, the latter through a 1,5-H transfer rearrangement mechanism. Evidences of the radical
nature of the reactions mechanism were provided by ESR spectroscopy, furthermore the same
technique, allowed to discover that the reaction of azides with indium trichloride and other group
XIII Lewis acids, in particular gallium trichloride, gives rise to strongly coloured, persistent
paramagnetic species, whose structure is consistent with the radical cation of the head-to-tail
dimer of the aniline corresponding to the starting azide.
| Identifer | oai:union.ndltd.org:unibo.it/oai:amsdottorato.cib.unibo.it:1052 |
| Date | 15 April 2008 |
| Creators | Bencivenni, Giorgio <1978> |
| Contributors | Nanni, Daniele |
| Publisher | Alma Mater Studiorum - Università di Bologna |
| Source Sets | Università di Bologna |
| Language | English |
| Detected Language | English |
| Type | Doctoral Thesis, PeerReviewed |
| Format | application/pdf |
| Rights | info:eu-repo/semantics/openAccess |
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