86359-47-9Relevant academic research and scientific papers
Rearrangement of α-hydroxy imines to α-amino ketones: Mechanistic aspects and synthetic applications
Compain,Gore,Vatele
, p. 6647 - 6664 (2007/10/03)
In refluxing diglyme, rearrangement of α-hydroxy imines bearing diversely substituted allyl groups or a 3-trimethylsilylpropargyl group on the α-carbon to the nitrogen afforded in good yields α-amino ketones. Migration of allyl or 3-trimethylsilylallyl groups occurred without allylic transposition in contrast to be 1-methylallyl group. In the 3 cases studied, the rearrangement of enantioenriched α-hydroxy imines took place with complete 1,2-chirality transfer. The rearrangement was applied to the preparation of (+)-1-benzyl-1-azaspiro[5.5]undecan-7-one, a precursor in the synthesis of (-)-perhydrohistrionicotoxin.
Highly regio- and stereoselective allylation of α-diketones via the fluorosilicate route
Gewald, Rainer,Kira, Mitsuo,Sakurai, Hideki
, p. 111 - 115 (2007/10/03)
A1lylation of enolizable α-diketones with allyltrifluorosilanes in the presence of triethylamine gave the corresponding tertiary homoallyl alcohols in good yield in a highly regio- and stereospecific manner. The reaction proceeds as diallylation with allyltrifluorosilanes yielding the 1,2-diols with high diastereoselectivity. The more sterically demanding crotyl- and prenyltrifluorosilanes lead exclusively to monoallylated products with the allyl group being added γ-regioselectively. In addition, highly diastereoselective crotylation was observed in the formation of the monoallylated α-hydroxy ketones. Asymmetric α-diketones were generally allylated at the less enolized ketone group except when both diketone and allylsilane were sterically hindered.
THERMAL REARRANGEMENT OF α-HYDROXY IMINES WITH AN α-ALLYL OR AN α-PROPARGYL SUBSTITUENT
Vatele, Jean-Michel,Dumas, Daniel,Gore, Jacques
, p. 2277 - 2280 (2007/10/02)
In refluxing diglyme, the title α-hydroxy imines 7 and 8 rearrange cleanly to amino ketones 9 and 10 substituted on the carbon α to nitrogen by an allyl or a propargyl group.In the case of α-hydroxy imine 9, the migration of the allyl group occurs with an allylic transposition.
