TY - JOUR
T1 - Catalyst-Dependent Rate-Determining Steps in Regiodivergent Vinylogous Aza-Morita-Baylis-Hillman Reactions with N-Ts Imines
AU - Gondo, Naruhiro
AU - Hyakutake, Ryuichi
AU - Fujimura, Koki
AU - Ueda, Yoshihiro
AU - Nakano, Katsuhiko
AU - Tsutsumi, Ryosuke
AU - Yamanaka, Masahiro
AU - Kawabata, Takeo
N1 - Funding Information:
This research was financially supported by Grants‐in‐Aids for Scientific Research S (JP26221301), Scientific Research C (JP20K06964), and Scientific Research on Innovative Areas “Middle Molecular Strategy” (JP18H04405) and “Hybrid Catalysis” (JP20H04828). N. G. acknowledges financial support from the JSPS Research Fellowship for Young Scientists (JP19J14988).
Publisher Copyright:
© 2021 Wiley-VCH GmbH
PY - 2022/3
Y1 - 2022/3
N2 - Catalyst-controlled vinylogous aza-MBH reactions of vinylcyclopentenone were performed, and it was found that the α-adducts were exclusively obtained by DABCO-catalysis, while the γ-adducts were the major products by DMAP-catalysis. We report here that the rate-determining step of the DABCO-catalyzed α-selective reactions is the Mannich-type C−C bond forming step, while that of the DMAP-catalyzed γ-selective reactions seems to be the β-elimination step.
AB - Catalyst-controlled vinylogous aza-MBH reactions of vinylcyclopentenone were performed, and it was found that the α-adducts were exclusively obtained by DABCO-catalysis, while the γ-adducts were the major products by DMAP-catalysis. We report here that the rate-determining step of the DABCO-catalyzed α-selective reactions is the Mannich-type C−C bond forming step, while that of the DMAP-catalyzed γ-selective reactions seems to be the β-elimination step.
KW - aza-Morita-Baylis-Hillman reaction
KW - kinetic isotope effect
KW - organocatalysis
KW - rate-determining step
KW - regioselectivity
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U2 - 10.1002/ajoc.202100533
DO - 10.1002/ajoc.202100533
M3 - Article
AN - SCOPUS:85120335280
SN - 2193-5807
VL - 11
JO - Asian Journal of Organic Chemistry
JF - Asian Journal of Organic Chemistry
IS - 3
M1 - e202100533
ER -