1. Cross-Aldol Reaction of Isatin with Acetone Catalyzed by Leucinol: A Mechanistic Investigation
Mikhail A Kabeshov, Ondřej Kysilka, Lubomír Rulíšek, Yury V Suleimanov, Marco Bella, Andrei V Malkov, Pavel Kočovský Chemistry. 2015 Aug 17;21(34):12026-33. doi: 10.1002/chem.201500536. Epub 2015 Jul 6.
Comprehensive mechanistic studies on the enantioselective aldol reaction between isatin (1 a) and acetone, catalyzed by L-leucinol (3 a), unraveled that isatin, apart from being a substrate, also plays an active catalytic role. Conversion of the intermediate oxazolidine 4 into the reactive syn-enamine 6, catalyzed by isatin, was identified as the rate-determining step by both the calculations (ΔG(≠) =26.1 kcal mol(-1) for the analogous L-alaninol, 3 b) and the kinetic isotope effect (kH /kD =2.7 observed for the reaction using [D6 ]acetone). The subsequent reaction of the syn-enamine 6 with isatin produces (S)-2 a (calculated ΔG(≠) =11.6 kcal mol(-1) ). The calculations suggest that the overall stereochemistry is controlled by two key events: 1) the isatin-catalyzed formation of the syn-enamine 6, which is thermodynamically favored over its anti-rotamer 7 by 2.3 kcal mol(-1) ; and 2) the high preference of the syn-enamine 6 to produce (S)-2 a on reaction with isatin (1 a) rather than its enantiomer (ΔΔG(≠) =2.6 kcal mol(-1) ).
2. SPF-5506-A4, a new peptaibol inhibitor of amyloid beta-peptide formation produced by Trichoderma sp
Nobuo Hosotani, Kazuo Kumagai, Shigeyuki Honda, Akira Ito, Takuro Shimatani, Ikutaro Saji J Antibiot (Tokyo). 2007 Mar;60(3):184-90. doi: 10.1038/ja.2007.20.
A new peptaibol compound, SPF-5506-A4, was isolated from the fermentation broth of Trichoderma sp. SPF-5506. The chemical structure of the 14-residue peptide was determined by MS, NMR and amino acid sequence analyses. The absolute configuration of amino acid residues in the acid hydrolysate was determined by Marfey's method. The structure of SPF-5506-A4 was established as Ac-Aib-L-Asn-L-Ile-Aib-L-Pro-L-Ser-L-Ile-Aib-L-Pro-L-Leu-L-Leu-Aib-L-Pro-L-leucinol. The compound inhibited amyloid beta-peptide formation in primary guinea pig cerebral cortex neuron cell culture dose-dependently with an IC50 of 0.1 microg/ml. Cytotoxicity was not observed at concentrations of <3 microg/ml.
3. Enantiopure tetranuclear iron(III) complexes using chiral reduced Schiff base ligands: synthesis, structure, spectroscopy, magnetic properties, and DFT studies
Reena Singh, Atanu Banerjee, Enrique Colacio, Kajal Krishna Rajak Inorg Chem. 2009 Jun 1;48(11):4753-62. doi: 10.1021/ic802206q.
Four new tetranuclear iron(III) complexes of formula [{Fe(L)(2)}(3)Fe], 1-4, have been prepared by reacting [Fe(ClO(4))(3)].6H(2)O with H(2)L in methanol. Here, L(2-) is the deprotonated form of N-(2-hyrdoxybenzyl)-l-valinol (H(2)L(1)), N-(2-hyrdoxybenzyl)-l-leucinol (H(2)L(2)), N-(5-chloro-2-hyrdoxybenzyl)-l-leucinol (H(2)L(3)), and N-(2-hyrdoxybenzyl)-l-phenylalaninol (H(2)L(4)). The complexes are prepared in an enantiomeric pure form. The complexes have been characterized with the help of IR, UV-vis, circular dichroism (CD), (1)H, and elemental analyses. The complex [{Fe(L(2))(2)}(3)Fe].CH(3)OH.2H(2)O, 2.CH(3)OH.2H(2)O, crystallizes in enantiomeric pure form containing a propeller-like Fe(4)O(6) core. (1)H and CD spectral studies of the four species are consistent with the structural similarities of the complexes in solution. Variable-temperature magnetic susceptibility of one case shows an intramolecular antiferromagnetic coupling between the Fe(III) ions. Magnetic measurements are in accord with the S = 5 ground state and suggest single molecular magnet behavior. The magnetic exchange coupling constant between the iron centers within the molecule is interpreted using broken-symmetry density functional theory calculation.
