ol503757h_si_001.pdf (3.77 MB)
Organo-Manganese η2‑Auxiliary Directed Reactions: A Diastereoselective Approach to 2,3-Allenols
journal contribution
posted on 2015-02-20, 00:00 authored by Animesh Roy, Bilal
A. Bhat, Salvatore D. LeporePropargyl
aldehydes underwent isomerization to allenyl aldehydes
under mildly basic conditions when complexed to an organo-manganese
auxiliary using methylcyclopentadienyl manganese tricarbonyl (MMT).
This traceless auxiliary magnifies the axial chirality of the allene
moiety, allowing for highly diastereoselective additions to the aldehyde
carbonyl and subsequent access to an array of 2,3-allenols. Using
this strategy, a nitrile-substituted 2,3-allenol was prepared and
efficiently converted to Hagen’s gland lactone.