Catalyst-Dependent Rate-Determining Steps in Regiodivergent Vinylogous Aza-Morita-Baylis-Hillman Reactions with N-Ts Imines

Naruhiro Gondo; Ryuichi Hyakutake; Koki Fujimura; Yoshihiro Ueda; Katsuhiko Nakano; Ryosuke Tsutsumi; Masahiro Yamanaka; Takeo Kawabata

doi:10.1002/ajoc.202100533

Catalyst-Dependent Rate-Determining Steps in Regiodivergent Vinylogous Aza-Morita-Baylis-Hillman Reactions with N-Ts Imines

Naruhiro Gondo, Ryuichi Hyakutake, Koki Fujimura, Yoshihiro Ueda, Katsuhiko Nakano, Ryosuke Tsutsumi, Masahiro Yamanaka, Takeo Kawabata

Research output: Contribution to journal › Article › peer-review

Abstract

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.

Original language	English
Article number	e202100533
Journal	Asian Journal of Organic Chemistry
Volume	11
Issue number	3
DOIs	https://doi.org/10.1002/ajoc.202100533
Publication status	Published - 2022 Mar
Externally published	Yes

Keywords

aza-Morita-Baylis-Hillman reaction
kinetic isotope effect
organocatalysis
rate-determining step
regioselectivity

ASJC Scopus subject areas

Organic Chemistry

Access to Document

10.1002/ajoc.202100533

Cite this

@article{a325e69da0b1495199be7c77ea691d55,

title = "Catalyst-Dependent Rate-Determining Steps in Regiodivergent Vinylogous Aza-Morita-Baylis-Hillman Reactions with N-Ts Imines",

abstract = "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.",

keywords = "aza-Morita-Baylis-Hillman reaction, kinetic isotope effect, organocatalysis, rate-determining step, regioselectivity",

author = "Naruhiro Gondo and Ryuichi Hyakutake and Koki Fujimura and Yoshihiro Ueda and Katsuhiko Nakano and Ryosuke Tsutsumi and Masahiro Yamanaka and Takeo Kawabata",

note = "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: {\textcopyright} 2021 Wiley-VCH GmbH",

year = "2022",

month = mar,

doi = "10.1002/ajoc.202100533",

language = "English",

volume = "11",

journal = "Asian Journal of Organic Chemistry",

issn = "2193-5807",

publisher = "Wiley - VCH Verlag GmbH & CO. KGaA",

number = "3",

}

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

UR - http://www.scopus.com/inward/record.url?scp=85120335280&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85120335280&partnerID=8YFLogxK

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 -

Catalyst-Dependent Rate-Determining Steps in Regiodivergent Vinylogous Aza-Morita-Baylis-Hillman Reactions with N-Ts Imines

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this