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

Published as part of the Special Topic Cobalt in Organic Synthesis

Abstract

The enantiopure salt ∆-[Co((S,S)-dpen)₃]³⁺ 2Cl^–BAr_f ^– [BAr_f = 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^–BAr_f20 ^– [BAr_f20 ^– = 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 anions

• References


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• 21 These compounds are available from many vendors. The best prices in effect as of the submission date of this manuscript are from Ark Pharm (http://www.arkpharminc.com) for R,R-dpen ($420/100 g) and Aris Pharmaceuticals (http://www.arispharma.com) for S,S-dpen ($408/100 g).
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