TY - JOUR
T1 - Enantioselective Halolactonization Reactions using BINOL-Derived Bifunctional Catalysts
T2 - Methodology, Diversification, and Applications
AU - Klosowski, Daniel W.
AU - Hethcox, J. Caleb
AU - Paull, Daniel H.
AU - Fang, Chao
AU - Donald, James R.
AU - Shugrue, Christopher R.
AU - Pansick, Andrew D.
AU - Martin, Stephen F.
N1 - Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/6/1
Y1 - 2018/6/1
N2 - A general protocol is described for inducing enantioselective halolactonizations of unsaturated carboxylic acids using novel bifunctional organic catalysts derived from a chiral binaphthalene scaffold. Bromo- and iodolactonization reactions of diversely substituted, unsaturated carboxylic acids proceed with high degrees of enantioselectivity, regioselectivity, and diastereoselectivity. Notably, these BINOL-derived catalysts are the first to induce the bromo- and iodolactonizations of 5-alkyl-4(Z)-olefinic acids via 5-exo mode cyclizations to give lactones in which new carbon-halogen bonds are created at a stereogenic center with high diastereo- and enantioselectivities. Iodolactonizations of 6-substituted-5(Z)-olefinic acids also occur via 6-exo cyclizations to provide δ-lactones with excellent enantioselectivities. Several notable applications of this halolactonization methodology were developed for desymmetrization, kinetic resolution, and epoxidation of Z-alkenes. The utility of these reactions is demonstrated by their application to a synthesis of precursors of the F-ring subunit of kibdelone C and to the shortest catalytic, enantioselective synthesis of (+)-disparlure reported to date.
AB - A general protocol is described for inducing enantioselective halolactonizations of unsaturated carboxylic acids using novel bifunctional organic catalysts derived from a chiral binaphthalene scaffold. Bromo- and iodolactonization reactions of diversely substituted, unsaturated carboxylic acids proceed with high degrees of enantioselectivity, regioselectivity, and diastereoselectivity. Notably, these BINOL-derived catalysts are the first to induce the bromo- and iodolactonizations of 5-alkyl-4(Z)-olefinic acids via 5-exo mode cyclizations to give lactones in which new carbon-halogen bonds are created at a stereogenic center with high diastereo- and enantioselectivities. Iodolactonizations of 6-substituted-5(Z)-olefinic acids also occur via 6-exo cyclizations to provide δ-lactones with excellent enantioselectivities. Several notable applications of this halolactonization methodology were developed for desymmetrization, kinetic resolution, and epoxidation of Z-alkenes. The utility of these reactions is demonstrated by their application to a synthesis of precursors of the F-ring subunit of kibdelone C and to the shortest catalytic, enantioselective synthesis of (+)-disparlure reported to date.
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U2 - 10.1021/acs.joc.8b00490
DO - 10.1021/acs.joc.8b00490
M3 - Article
C2 - 29717607
AN - SCOPUS:85046673540
SN - 0022-3263
VL - 83
SP - 5954
EP - 5968
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 11
ER -