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OH‐Directed Alkynylation of 2‐Vinylphenols with Ethynyl Benziodoxolones: A Fast Access to Terminal 1,3‐Enynes
Author(s) -
Finkbeiner Peter,
Kloeckner Ulrich,
Nachtsheim Boris J.
Publication year - 2015
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.201412148
Subject(s) - hypervalent molecule , chemoselectivity , alkynylation , reagent , chemistry , iodine , stereoselectivity , combinatorial chemistry , catalysis , stereochemistry , organic chemistry
The first direct alkynylation of 2‐vinylphenols was developed. The rationally optimized hypervalent iodine reagent TIPS‐EBX* in combination with [(Cp*RhCl 2 ) 2 ] as a CH‐activating transition metal catalyst enables the construction of a variety of highly substituted 1,3‐enynes in high yields of up to 98 %. This novel CH activation method shows excellent chemoselectivity and exclusive ( Z )‐stereoselectivity, and it is also remarkably mild and tolerates a variety of functional groups. Furthermore, synthetic modifications of the resulting 1,3‐enynes were demonstrated. To our knowledge, this is the first example for an OH‐directed CH alkynylation with hypervalent iodine reagents.