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Hydroxy‐Directed Ruthenium‐Catalyzed Alkene/Alkyne Coupling: Increased Scope, Stereochemical Implications, and Mechanistic Rationale
Author(s) -
Rummelt Stephan M.,
Cheng GuiJuan,
Gupta Puneet,
Thiel Walter,
Fürstner Alois
Publication year - 2017
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.201700342
Subject(s) - alkyne , alkene , regioselectivity , propargyl , ruthenium , chemistry , enyne , catalysis , stereochemistry , ligand (biochemistry) , combinatorial chemistry , substrate (aquarium) , intermolecular force , diene , molecule , organic chemistry , receptor , biochemistry , oceanography , natural rubber , geology
The recognition of the dual binding mode of propargyl and allyl alcohols to [Cp*Ru] fragments fostered the development of a highly regioselective intermolecular Alder‐ene‐type reaction of alkynes with 1,2‐disubstituted alkenes. The increased substrate scope opens new perspectives in stereochemical terms. As the loaded catalyst is chiral‐at‐metal, stereochemical information is efficiently relayed from the propargylic site to the emerging C−C bond. This interpretation is based on the X‐ray structure of the first Cp*Ru complex carrying an intact enyne ligand, and provides valuable insights into bonding and activation of the substrates. Computational data draw a clear picture of the principles governing regio‐ and stereocontrol.