164220-99-9

Upstream product

• 169737-45-5 (1S,4R)-4,7,7-Trimethyl-3-oxo-2-oxa-bicyclo[2.2.1]heptane-1-carboxylic acid (R)-2-oxo-1-(3-trimethylsilanyl-prop-2-ynyl)-cyclohexyl ester 
• 164220-97-7 (R)-2-Hydroxy-2-(3-trimethylsilanyl-prop-2-ynyl)-cyclohexanone 
• 51128-50-8 2-[(trimethylsilyl)oxy]cyclohex-2-en-1-one 
• 164220-98-8 (R)-2-[(Z)-Benzylimino]-1-(3-trimethylsilanyl-prop-2-ynyl)-cyclohexanol 
• 765-87-7 cyclohexane-1,2-dione 

Downstream Products

• 164221-00-5 (-)-(Z)-2-benzylamino-2-(3-trimethylysilylprop-2-ynyl)cyclohexanone 

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.

Thermal Rearrangement of Enantioenriched α-Hydroxy Imines -II. Formal Synthesis of (-)-Perhydrohistrionicotoxin.

Synthesis of (+)-1-benzyl-1-azaspiroundecan-7-one 6 from α-ketol 1, via a 1,2-suprafacial chirality transfer, is described.