Isothiourea-Mediated Asymmetric
Functionalization
of 3‑Alkenoic Acids

Morrill, Louis
C.; Smith, Samuel M.; M. Z. Slawin, Alexandra; Smith, Andrew D.

doi:10.1021/jo402591v.s006

jo402591v_si_006.pdf (2.94 MB)

Isothiourea-Mediated Asymmetric Functionalization of 3‑Alkenoic Acids

journal contribution

posted on 2014-02-21, 00:00 authored by Louis C. Morrill, Samuel M. Smith, Alexandra M. Z. Slawin, Andrew D. Smith

Isothiourea HBTM-2.1 promotes the catalytic asymmetric α-functionalization of 3-alkenoic acids through formal [2 + 2] cycloadditions with N-tosyl aldimines and formal [4 + 2] cycloadditions with either 4-aryltrifluoromethyl enones or N-aryl-N-aroyl diazenes, providing useful synthetic building blocks in good yield and with excellent enantiocontrol (up to >99% ee). Stereodefined products are amenable to further synthetic elaboration through manipulation of the olefinic functionality.