128939-26-4

Upstream product

• 86359-45-7 2-hydroxy-2-(2-methylprop-2-enyl)cyclohexanone 
• 100-46-9 benzylamine 
• 765-87-7 cyclohexane-1,2-dione 
• 51128-50-8 2-[(trimethylsilyl)oxy]cyclohex-2-en-1-one 
• 128939-16-2 2-[(Z)-Benzylimino]-1-(2-methyl-allyl)-cyclohexanol 
• 144079-92-5 Benzyl-[2-(2-methyl-allyloxy)-cyclohex-(E)-ylidene]-amine 
• 128939-16-2 2-[(E)-Benzylimino]-1-(2-methyl-allyl)-cyclohexanol 

Relevant academic research and scientific papers

Rearrangement of α-hydroxy imines to α-amino ketones: Mechanistic aspects and synthetic applications

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.

A facile Claisen rearrangement involving the transient tautomeric enamine forms of α-allyloxy and α-propargyloxyimines

α-Allyloxyimines rearrange smoothly to 2-amino-2-allyl-ketones by heating at 80°C for few hours, by Claisen rearrangement of the tautomeric secondary enamine. Similarly α-propargyloxyimine gave 2-amino-2-allenyl-ketones. By contrast, 2-benzyloxyimines aff

THERMAL REARRANGEMENT OF α-HYDROXY IMINES WITH AN α-ALLYL OR AN α-PROPARGYL SUBSTITUENT

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.