TY - JOUR
T1 - DyKAT by DiCat
T2 - Stereoconvergent Dienamine-Catalyzed Claisen Rearrangements
AU - De Oliveira Silva, Ana
AU - Harper, Jordan L.
AU - Fuhr, Katherine N.
AU - Lalancette, Roger A.
AU - Cheong, Paul Ha Yeon
AU - Brenner-Moyer, Stacey E.
N1 - Funding Information:
This work was supported by the National Science Foundation (S.E.B.M., CHE-1955044; A.D.O.S., AGEP-Graduate Research Supplement to CHE-1955044). P.H.Y.C. is the Bert and Emelyn Christensen professor of OSU, and gratefully acknowledges financial support from the Vicki & Patrick F. Stone family and the National Science Foundation (NSF, CHE-1352663). Acquisition of X-ray crystallography data for this study was supported by an NSF-MRI grant (CHE-2018753). The authors also thank Mr. Furong Sun (University of Illinois) for the acquisition of mass spectrometry data.
Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
PY - 2022/8/5
Y1 - 2022/8/5
N2 - This Claisen rearrangement establishes the feasibility of DyKAT of γ-epimeric enals via dienamine formation to afford enantioenriched products. γ-Aryl and -alkyl enals, and exocyclic enals that introduce quaternary centers, are all amenable substrates. Products are readily converted into pyrrolidines or cyclopentenols. Notably, a reactive dienamine intermediate has been isolated from a catalytic reaction, fully characterized, and converted to product upon reexposure to reaction conditions. Product configuration arises from a directing C-H···πinteraction in the transition state.
AB - This Claisen rearrangement establishes the feasibility of DyKAT of γ-epimeric enals via dienamine formation to afford enantioenriched products. γ-Aryl and -alkyl enals, and exocyclic enals that introduce quaternary centers, are all amenable substrates. Products are readily converted into pyrrolidines or cyclopentenols. Notably, a reactive dienamine intermediate has been isolated from a catalytic reaction, fully characterized, and converted to product upon reexposure to reaction conditions. Product configuration arises from a directing C-H···πinteraction in the transition state.
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U2 - 10.1021/acs.joc.2c01079
DO - 10.1021/acs.joc.2c01079
M3 - Article
AN - SCOPUS:85135960973
SN - 0022-3263
VL - 87
SP - 10105
EP - 10113
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 15
ER -