TY - JOUR
T1 - Merging of Light/Dark Palladium Catalytic Cycles Enables Multicomponent Tandem Alkyl Heck/Tsuji-Trost Homologative Amination Reaction toward Allylic Amines
AU - Kvasovs, Nikita
AU - Fang, Jian
AU - Kliuev, Fedor
AU - Gevorgyan, Vladimir
N1 - Funding Information:
We thank the National Institutes of Health (GM120281), National Science Foundation (CHE-2246075), and Welch Foundation (Chair, AT-0041) for financial support.
Publisher Copyright:
© 2023 American Chemical Society.
PY - 2023/8/23
Y1 - 2023/8/23
N2 - A visible light-induced palladium-catalyzed homologative three-component synthesis of allylic amines has been developed. This protocol proceeds via a unique mechanism involving two distinct cycles enabled by the same Pd(0) catalyst: a visible light-induced hybrid radical alkyl Heck reaction between 1,1-dielectrophile and styrene, followed by the “in dark” classical Tsuji-Trost-type allylic substitution reaction. This method works well with a broad range of primary and secondary amines, aryl alkenes, dielectrophiles, and in complex settings. The regiochemistry of the obtained products is primarily governed by the structure of 1,1-dielectrophile. Involvement of π-allyl palladium intermediates allowed for the control of stereoselectivity, which has been demonstrated with up to 95:5 er.
AB - A visible light-induced palladium-catalyzed homologative three-component synthesis of allylic amines has been developed. This protocol proceeds via a unique mechanism involving two distinct cycles enabled by the same Pd(0) catalyst: a visible light-induced hybrid radical alkyl Heck reaction between 1,1-dielectrophile and styrene, followed by the “in dark” classical Tsuji-Trost-type allylic substitution reaction. This method works well with a broad range of primary and secondary amines, aryl alkenes, dielectrophiles, and in complex settings. The regiochemistry of the obtained products is primarily governed by the structure of 1,1-dielectrophile. Involvement of π-allyl palladium intermediates allowed for the control of stereoselectivity, which has been demonstrated with up to 95:5 er.
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U2 - 10.1021/jacs.3c04968
DO - 10.1021/jacs.3c04968
M3 - Article
C2 - 37556443
AN - SCOPUS:85168365767
SN - 0002-7863
VL - 145
SP - 18497
EP - 18505
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 33
ER -