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NHC‐Organocatalyzed C Ar −O Bond Cleavage: Mild Access to 2‐Hydroxybenzophenones
Author(s) -
JanssenMüller Daniel,
Singha Santanu,
Lied Fabian,
Gottschalk Karin,
Glorius Frank
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.201610203
Subject(s) - cleavage (geology) , bond cleavage , chemistry , catalysis , materials science , organic chemistry , fracture (geology) , composite material
A Truce–Smiles rearrangement of acyl‐anion equivalents generated by N‐heterocyclic carbene (NHC) catalysis has been achieved. The developed method includes C Ar −O, C Ar −S, or C Ar −N bond cleavage for the formation of a C Ar −C bond and enables access to 2‐hydroxybenzophenones, an important structural motif that is present in several bioactive natural products. By utilizing this procedure, the alkaloid taxilamine was synthesized in three steps. DFT calculations and control experiments support a classical S N Ar mechanism with a catalyst‐bound Meisenheimer‐type intermediate. The method features mild reaction conditions, excellent functional‐group tolerance, and a broad substrate scope, including various classes of (hetero)arenes.