Trinuclear C-3-Symmetric Extension of Jacobsen's Catalyst: Synthesis, Characterization, and Catalytic Properties of a Chiral Trinuclear Mn-III Triplesalen Complex

Mukherjee C, Stammler A, Bögge H, Glaser T (2009)
INORGANIC CHEMISTRY 48(19): 9476-9484.

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Abstract
The synthesis of a chiral version of a triplesalen ligand has been performed in two steps starting from 2,4,6-triacetyl-1,3,5-trihydroxybenzene (1). Reaction with excess trans-(1R,2R)-12-cyclohexanediamine and trans-(1S,2S)-1,2-cyclohexanediamine provided the chiral triplesalen half units 2,4,6-tris[1-((1R,2R)-2-aminocyclohexylimino)ethyl]-1,3,5-trihydroxybenz ene (2(RR)) and 2,4,6-tris[1-((1S, 2S)-2-aminocyclohexylilnino)ethyl]-13,5-trihydroxybenzene (2(SS)), respectively. The two enantiomeric pure triplesalen ligands H(6)chand(RR) and H(6)chand(SS) were obtained by reaction of the triplesalen half units with 3,5-di-tert-butylsalicylaldehyde. Reaction with MnCl2 center dot 2H(2)O under basic aerobic conditions afforded the chiral trinuclear triplesalen complexes 3(RR) and 3(SS). Single-crystal X-ray diffraction studies on both enantiomers showed the presence of the two ionization isomers [(chand){(MnCl)-Cl-III(MeOH)}(3)] and [(chand){Mn-III(MeOH)(2)}(3)]Cl-3 in the solid state, resulting in the formulation of 3 (either 3(RR) or 3(SS)) as [(chand){(MnCl)-Cl-III(MeOH)}(3)][(chand){Mn-III(MeOH)(2)}(3)]Cl-3. The crystal structures exhibit chiral hydrophobic channels of similar to 8 angstrom diameter decorated with tert-butyl groups. These form left-handed helices in the 3(RR) enantiomer and right-handed helices in the 3(SS) enantiomer. Magnetic measurements are in accord with weak exchange interactions between the Mn-III S-i = 2 ions and strong local magnetic anisotropy as has been found in other trinuclear Mn-3(III) triplesalen complexes. As a proof-of principal, we have investigated the catalytic ability of the two enantiomers in the enantioselective epoxidation of unfunctionalized olefins. The chiral trinuclear Mn-3(III) triplesalen acts under nonoptimized conditions as a catalyst with relatively good yields and moderate enantiomeric excess.
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Mukherjee C, Stammler A, Bögge H, Glaser T. Trinuclear C-3-Symmetric Extension of Jacobsen's Catalyst: Synthesis, Characterization, and Catalytic Properties of a Chiral Trinuclear Mn-III Triplesalen Complex. INORGANIC CHEMISTRY. 2009;48(19):9476-9484.
Mukherjee, C., Stammler, A., Bögge, H., & Glaser, T. (2009). Trinuclear C-3-Symmetric Extension of Jacobsen's Catalyst: Synthesis, Characterization, and Catalytic Properties of a Chiral Trinuclear Mn-III Triplesalen Complex. INORGANIC CHEMISTRY, 48(19), 9476-9484.
Mukherjee, C., Stammler, A., Bögge, H., and Glaser, T. (2009). Trinuclear C-3-Symmetric Extension of Jacobsen's Catalyst: Synthesis, Characterization, and Catalytic Properties of a Chiral Trinuclear Mn-III Triplesalen Complex. INORGANIC CHEMISTRY 48, 9476-9484.
Mukherjee, C., et al., 2009. Trinuclear C-3-Symmetric Extension of Jacobsen's Catalyst: Synthesis, Characterization, and Catalytic Properties of a Chiral Trinuclear Mn-III Triplesalen Complex. INORGANIC CHEMISTRY, 48(19), p 9476-9484.
C. Mukherjee, et al., “Trinuclear C-3-Symmetric Extension of Jacobsen's Catalyst: Synthesis, Characterization, and Catalytic Properties of a Chiral Trinuclear Mn-III Triplesalen Complex”, INORGANIC CHEMISTRY, vol. 48, 2009, pp. 9476-9484.
Mukherjee, C., Stammler, A., Bögge, H., Glaser, T.: Trinuclear C-3-Symmetric Extension of Jacobsen's Catalyst: Synthesis, Characterization, and Catalytic Properties of a Chiral Trinuclear Mn-III Triplesalen Complex. INORGANIC CHEMISTRY. 48, 9476-9484 (2009).
Mukherjee, Chandan, Stammler, Anja, Bögge, Hartmut, and Glaser, Thorsten. “Trinuclear C-3-Symmetric Extension of Jacobsen's Catalyst: Synthesis, Characterization, and Catalytic Properties of a Chiral Trinuclear Mn-III Triplesalen Complex”. INORGANIC CHEMISTRY 48.19 (2009): 9476-9484.
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