HMPA promotes retro-aldol reaction, resulting in syn-selective addition of lithiated 1-naphthylacetonitrile to aromatic aldehydes
In HMPA-THF solution, lithiated 1-naphthylacetonitrile undergoes highly syn-selective addition to aromatic aldehydes, providing the first access to such syn-aldols. Syn-selectivity is also observed with two other arylacetonitriles. Aldolate equilibration and crossover experiments demonstrate that HMPA promotes retro-aldol reaction and that aldol diastereoselectivity under these conditions is thermodynamically controlled.
Carlier
PR
Department of Chemistry, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong.
Lo
CW
Lo
MM
Wan
NC
Williams
ID