Premium
Directed Remote Lateral Metalation: Highly Substituted 2‐Naphthols and BINOLs by In Situ Generation of a Directing Group
Author(s) -
Patel Jignesh J.,
Laars Marju,
Gan Wei,
Board Johnathan,
Kitching Matthew O.,
Snieckus Victor
Publication year - 2018
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.201805203
Subject(s) - metalation , chemistry , in situ , ring (chemistry) , aryl , functional group , lithium (medication) , group (periodic table) , combinatorial chemistry , transmetalation , sequence (biology) , stereochemistry , organic chemistry , catalysis , biochemistry , alkyl , medicine , endocrinology , polymer
A general synthesis of highly substituted 2‐naphthols based on a new carbanionic reaction sequence is demonstrated. The reaction exploits the dual nature of lithium bases consisting of consecutive ring opening of readily available coumarins with either LiNEt 2 or LiN i Pr 2 into Z ‐cinnamamides, thus generating a directing group in situ and allowing, by conformational freedom, a lateral directed remote metalation for ring closure to give the aryl 2‐naphthols in good to excellent yields. These transformations can be combined to provide a more efficient one‐pot process. Mechanistic insight into the remote lateral metalation step, demonstrating the requirement of Z ‐cinnamamide, is described. Application of this methodology to the synthesis of highly substituted 3,3′‐diaryl BINOL ligands is also reported.