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Manganese(I)‐Catalyzed C−H Activation: The Key Role of a 7‐Membered Manganacycle in H‐Transfer and Reductive Elimination
Author(s) -
Yahaya Nasiru P.,
Appleby Kate M.,
Teh Magdalene,
Wagner Conrad,
Troschke Erik,
Bray Joshua T. W.,
Duckett Simon B.,
Hammarback L. Anders,
Ward Jonathan S.,
Milani Jessica,
Pridmore Natalie E.,
Whitwood Adrian C.,
Lynam Jason M.,
Fairlamb Ian J. S.
Publication year - 2016
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.201606236
Subject(s) - reductive elimination , chemistry , pyridinium , manganese , catalysis , regioselectivity , substrate (aquarium) , electron transfer , reactive intermediate , combinatorial chemistry , medicinal chemistry , stereochemistry , photochemistry , organic chemistry , oceanography , geology
Manganese‐catalyzed C−H bond activation chemistry is emerging as a powerful and complementary method for molecular functionalization. A highly reactive seven‐membered Mn I intermediate is detected and characterized that is effective for H‐transfer or reductive elimination to deliver alkenylated or pyridinium products, respectively. The two pathways are determined at Mn I by judicious choice of an electron‐deficient 2‐pyrone substrate containing a 2‐pyridyl directing group, which undergoes regioselective C−H bond activation, serving as a valuable system for probing the mechanistic features of Mn C−H bond activation chemistry.