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A Highly Efficient Dimeric Manganese‐Catalyzed Selective Hydroarylation of Internal Alkynes
Author(s) -
Pang Yubo,
Liu Gengtu,
Huang Congcong,
Yuan XiangAi,
Li Weipeng,
Xie Jin
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202004950
Subject(s) - catalysis , chemoselectivity , regioselectivity , steric effects , manganese , propargyl , chemistry , combinatorial chemistry , rhodium , palladium , ligand (biochemistry) , propargyl alcohol , functional group , transition metal , organic chemistry , biochemistry , polymer , receptor
We have developed a general and site‐predictable manganese‐catalyzed hydroarylation of internal alkynes in the presence of water, under an air atmosphere without the involvement of ligand. The unique catalytic feature of this reaction is highlighted by comparison with other widely used transition metal catalysts including palladium, rhodium, nickel, or copper. The simple operation, high efficiency and excellent functional group compatibility make this protocol practical for more than 90 structurally diverse internal alkynes, overcoming the influence of both electronic and steric effect of alkynes. Its exclusive regio‐ and chemoselectivity originates from the unique reactivity of the manganese‐based catalyst towards an inherent double controlled strategy of sterically hindered propargyl alcohols without the installing of external directing groups. Its synthetic robustness and practicality have been illustrated by the concise synthesis of bervastatin, a hypolipidemic drug, and late‐stage modification of complex alkynes with precise regioselectivity.