Synthesis of new binol based [1+1] macrocyclic chiral manganese(III) Schiff bases as catalysts for asymmetric epoxidation

A series of new chiral binol based [1+1] macrocyclic Schiff bases have been synthesized in high yields in short reaction times via cyclo-condensation of dialdehydes with long tethers and chiral diamines. Macrocyclic Mn(salen) complexes containing N2O2 salen units incorporated with spacers of increased tether lengths were synthesized and characterized. The newly synthesized catalyst system was successfully employed for the enantioselective epoxidation of unfunctionalized olefins with high yields and good enantioselectivity.

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Bis((S)-3′-formyl-2′-hydroxy-1,1′-binaphthyl-2-yl) succinateC46H30O8[α]D25=-152.3 (c 0.65, CHCl3)Source of chirality: (S)-binolAbsolute configuration: (1′S,1″S)

Bis((S)-3′-formyl-2′-hydroxy-1,1′-binaphthyl-2-yl) glutarateC47H32O8[α]D25=-221 (c 1.4, CH2Cl3)Source of chirality: (S)-binolAbsolute configuration: (1′S,1″S)

Bis((S)-3′-formyl-2′-hydroxy-1,1′-binaphthyl-2-yl) adipateC48H34O8[α]D25=-40.1 (c 0.4, CHCl3)Source of chirality: (S)-binolAbsolute configuration: (1′S,1″S)

(S)-2′-Formyl-3′-hydroxy-1,1′-binaphthyl-2-yl acetateC23H16O4[α]D25=-123.8 (c 0.82, CHCl3)Source of chirality: (S)-binolAbsolute configuration: (S)

C52H40N2O6[α]D25=-642 (c 1.0, CHCl3)Source of chirality: (S)-binol and (1R,2R)-diammoniumcyclohexane mono-(+)-tartrateAbsolute configuration: (1′S,1″S), (1R,2R)

C57H43N3O6[α]D25=-20.6 (c 0.2, CHCl3)Source of chirality: (S)-binol and (3R,4R)-1-benzylpyrrolidine-3,4-diaminium chlorideAbsolute configuration: (1′S,1″S), (3R,4R)

C64H50N2O8[α]D25=-312.5 (c 1.0, CHCl3)Source of chirality: (S)-binol and (2S,3S)-1,4bis(benzyloxy)-2,3-diaminobutane hydrochlorideAbsolute configuration: (1′S,1″S), (2S,3S)

C53H42N2O6[α]D25=-123.8 (c 0.3, CHCl3)Source of chirality: (S)-binol and (1R,2R)-diammoniumcyclohexane mono-(+)-tartrateAbsolute configuration: (1′S,1″S), (1R,2R)

C65H52N2O8[α]D25=-195.3 (c 0.63, CHCl3)Source of chirality: (S)-binol and (2S,3S)-1,4bis(benzyloxy)-2,3-diaminobutane hydrochlorideAbsolute configuration: (1′S,1″S), (2S,3S)

C54H44N2O6[α]D25=-185.4 (c 0.3 CHCl3)Source of chirality: (S)-binol and (1R,2R)-diammoniumcyclohexane mono-(+)-tartrateAbsolute configuration: (1′S,1″S), (1R,2R)

C59H47N3O6[α]D25=-256.4 (c 0.73, CHCl3)Source of chirality: (S)-binol and (3R,4R)-1-benzylpyrrolidine-3,4-diaminium chlorideAbsolute configuration: (1′S,1″S), (3R,4R)

C66H54N2O8[α]D25=-149.8 (c 0.1, CHCl3)Source of chirality: (S)-binol and (2S,3S)-1,4-bis(benzyloxy)-2,3-diaminobutane hydrochlorideAbsolute configuration: (1′S,1″S), (2S,3S)

C52H38ClMnN2O6[α]D25=-43.6 (c 0.2, CHCl3)Source of chirality: (S)-binol and (1R,2R)-diammoniumcyclohexane mono-(+)-tartrateAbsolute configuration: (1′S,1″S), (1R,2R)

C53H40ClMnN2O6[α]D25=-123.5 (c 0.52, CHCl3)Source of chirality: (S)-binol and (1R,2R)-diammoniumcyclohexane mono-(+)-tartrateAbsolute configuration: (1′S,1″S), (1R,2R)

C54H42ClMnN2O6[α]D25=-19.5 (c 0.1, CHCl3)Source of chirality: (S)-binol and (1R,2R)-diammoniumcyclohexane mono-(+)-tartrateAbsolute configuration: (1′S,1″S), (1R,2R)