TY - JOUR T1 - 1,3-Dienones and 2H-Pyran-2-ones from Soft α-Vinyl Enolization of β-Chlorovinyl Ketones: Defined Roles of Brönsted and Lewis Base. AU - Kim,Hun Young, AU - Oh,Kyungsoo, Y1 - 2015/12/09/ PY - 2015/12/10/entrez PY - 2015/12/10/pubmed PY - 2016/4/30/medline SP - 6254 EP - 7 JF - Organic letters JO - Org Lett VL - 17 IS - 24 N2 - The eliminative reaction pathways of (E)-β-chlorovinyl ketones were investigated in the presence of both Brönsted and Lewis bases. The Brönsted base, Et3N, effected the soft α-vinyl enolization of (E)-β-chlorovinyl ketones to [3]cumulenol intermediates; in turn, a catalytic amount of Lewis base, PPh3, initiated isomerization to provide 1,3-dienones in high yields. The introduction of a carbon-based nucleophile into the reaction mixture provided the highly efficient synthetic route to 2H-pyran-2-ones in one pot, where the carbon-based nucleophile generated by an extra equivalent of Brönsted base, Et3N, attacked the electrophilic [3]cumulenol intermediates to initiate cyclization to give 2H-pyran-2-ones. SN - 1523-7052 UR - https://www.unboundmedicine.com/medline/citation/26649772/13_Dienones_and_2H_Pyran_2_ones_from_Soft_α_Vinyl_Enolization_of_β_Chlorovinyl_Ketones:_Defined_Roles_of_Brönsted_and_Lewis_Base_ DB - PRIME DP - Unbound Medicine ER -