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DOI: 10.1055/s-0036-1590502
Enantioselective Additions of Stabilized Carbanions to Imines Generated from α-Amido Sulfones By Using Lipophilic Salts of Chiral Tris(1,2-diphenylethylenediamine) Cobalt(III) Trications as Hydrogen Bond Donor Catalysts
We thank the Welch Foundation (Grant A-1656) for support.Publication History
Received: 10 April 2017
Accepted after revision: 04 May 2017
Publication Date:
13 June 2017 (online)
![](https://www.thieme-connect.de/media/synthesis/201717/lookinside/thumbnails/ss-2017-c0236-st_10-1055_s-0036-1590502-1.jpg)
Published as part of the Special Topic Cobalt in Organic Synthesis
Abstract
The enantiopure salt ∆-[Co((S,S)-dpen)3]3+ 2Cl–BArf – [BArf = B(3,5-C6H3(CF3)2)4] is an effective hydrogen bond donor catalyst (10 mol%, r.t., CH2Cl2) for enantioselective additions of dialkyl malonates to Boc-derivatized aryl imines generated from sulfones [ArCH(SO2Ph)NHBoc] in the presence of K2CO3 (ten examples, 91–97% isolated yields, 87–99% ee). The diastereomeric salt Λ-[Co((S,S)-dpen)3]3+ 2Cl–BArf20 – [BArf20 – = B(C6F5)4 –] is similarly applied to additions of nitroalkanes (four examples, 89–93% isolated yields, 79–91% ee). Precautions to exclude air or moisture are unnecessary.
Key words
Werner complexes - cobalt - 1,2-diamine ligands - chiral-at-metal complexes - hydrogen bonding - enantioselective catalysis - chiral benzylic amines - lipophilic anionsSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1590502.
- Supporting Information
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Reviews:
For representative Mannich reactions involving Boc derivatives ArCH=NBoc and hydrogen bond donor catalysts, see:
For representative aza-Henry reactions involving Boc derivatives ArCH=NBoc and hydrogen bond donor catalysts, see:
For representative studies with metal-based catalysts, see:
For general experimental conditions, see the supporting information of the following two references:
Full papers detailing catalyst syntheses:
One representative computational investigation from several research groups: