Studies on the Bisoxazoline- and (−)-Sparteine-Mediated Enantioselective Addition of Organolithium Reagents to Imines

Studies on the Bisoxazoline- and (−)-Sparteine-Mediated Enantioselective Addition of Organolithium Reagents to Imines

The enantioselective addition of organolithium reagents to N‐anisylaldimines promoted by chiral bisoxazolines and (−)‐sparteine as external ligands is described. This reaction proceeds readily with a wide range of aldimine substrates (aliphatic, aromatic, olefinic) and organolithium nucleophiles (Me...

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Veröffentlicht in:Advanced synthesis & catalysis 2008-05, Vol.350 (7-8), p.1023-1045
Hauptverfasser: Denmark, Scott E., Nakajima, Noriyuki, Stiff, Cory M., Nicaise, Olivier J.-C., Kranz, Michael
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Sprache:eng
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aldimines
bisoxazolines
catalysis
enantioselective addition
organolithium reagents
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container_end_page 1045
container_issue 7-8
container_start_page 1023
container_title Advanced synthesis & catalysis
container_volume 350
creator Denmark, Scott E.
Nakajima, Noriyuki
Stiff, Cory M.
Nicaise, Olivier J.-C.
Kranz, Michael
description The enantioselective addition of organolithium reagents to N‐anisylaldimines promoted by chiral bisoxazolines and (−)‐sparteine as external ligands is described. This reaction proceeds readily with a wide range of aldimine substrates (aliphatic, aromatic, olefinic) and organolithium nucleophiles (Me, n‐Bu, Ph, vinyl) in excellent yields (81–99%) and with high enantioselectivities (up to 97:3.0 er). The external ligands can be used in substoichiometric amounts albeit with slightly attenuated enantioselectivities. A systematic evaluation of the structural features of the bisoxazolines revealed a primary contribution from the substituent at C(4) and a secondary influence from the bridging substituents. A computational analysis (PM3) provided a clear rationalization for the origin of enantioselectivity.
doi_str_mv 10.1002/adsc.200800017
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source Wiley Online Library Journals Frontfile Complete
subjects aldimines
bisoxazolines
catalysis
enantioselective addition
organolithium reagents
title Studies on the Bisoxazoline- and (−)-Sparteine-Mediated Enantioselective Addition of Organolithium Reagents to Imines
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