The direct synthesis of the title amino acid derivatives from carboxylic esters and nitrones can be achieved in fair to good yields when lithium or magnesium ester enolates were treated with nitrones in THF at -78 °C or in Et2O at -20 to 0 °C, respectively. The products from the reaction of t-butyl acetate with 3,4-dihydroisoquinoline N-oxide or 5,5-dimethylpyrroline 1-oxide were transformed into (1,2,3,4-tetrahydroisoquinolin-1-ylidene)acetate or (pyrrolidin-2-ylidene)acetate derivatives in the presence of triphenylphosphine, carbon tetrachloride, and triethylamine in refluxing dichloromethane.
When 1-(2-isocyanophenyl)pyrrole was treated with a catalytic amount of boron trifluoride, pyrrolo[1,2-a] quinoxaline was obtained almost quantitatively. The reaction in the presence of aldehydes or ketones gave the corresponding 4-(1-hydroxyalkyl)pyrrolo[1,2-a]quinoxalines in moderate to good isolated yields.
1-(2-Isocyanophenyl)pyrroles have been prepared. They react in moderate to good isolated yields with aldehydes (or ketones), oxiranes, and acetals in the presence of catalytic amounts of diethyl ether–boron trifluoride to give pyrrolo[1,2-a]quinoxalines carrying an oxyalkyl substituent, such as α-hydroxyalkyl, β-hydroxyalkyl, or α-alkoxyalkyl, at the 4-position.
The reaction of cyclopropyl phenyl sulfoxide with a magnesium amide, generated from ethylmagnesium bromide and diisopropylamine, gave 1-(phenylthio)cyclopropanol in 72% yield. When the diisopropylmagnesium reagent was treated with a thiol prior to an interaction with cyclopropyl phenyl sulfoxides, symmetrical and unsymmetrical cyclopropanone dithioacetals were produced in fair yields along with small quantities of the corresponding 1-(phenylthio)cyclopropanols.
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