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Axially chiral tridentate isoquinoline derived ligands for diethylzinc addition to aldehydes

Author:
Sweetman, Brian A., Guiry, Patrick J.
Source:
Tetrahedron 2018 v.74 no.38 pp. 5567-5581
ISSN:
0040-4020
Subject:
acids, aldehydes, catalysts, chemical reactions, chemical structure, chlorides, high performance liquid chromatography, ligands, phenol
Abstract:
The synthesis and resolution of new tridentate isoquinoline-derived ligands has been developed. The key steps in the synthetic sequence include successive, chemo-selective Suzuki-Miyaura cross-couplings of 1,3-dichloroisoquinoline with suitable arylboronic acids. The new ligands prepared in this manner were resolved either via molecular complexation with N-benzylcinchonidinium chloride as with 1-[3-(2-hydroxyphenyl)isoquinolin-1-yl]naphthalen-2-ol or via chromatographic separation of its epimeric camphorsulfonates as for 1,3-bis-(2-hydroxynaphthalen-1-yl)isoquinoline. 4-tert-Butyl-2-chloro-6-[1-(2-hydroxymethylnaphthalen-1-yl)isoquinolin-3-yl]phenol was resolved by chiral semi-preparative HPLC. The application of these ligands in the diethylzinc addition to aldehydes was investigated. In certain cases, the desired secondary alcohols were obtained in high yield with excellent enantiomeric excess (ee > 99%) at low catalyst loading (1 mol%).
Agid:
6103552