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Synthesis and characterization of both enantiomers of a chiral C60 derivative with C2 symmetry

The addition of chiral diamines to C60 allows the synthesis of the two enantiomers of a chiral C60 derivative with C2 symmetry. The circular dichroism spectra of the two isomers show a very intense chirospectroscopic response.

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Planar chiral ferrocene salen-type ligands featuring additional central and axial chirality

We report on novel chiral tridentate [NO2]H2 and tetradentate [N2O2]H2 Schiff base ligands containing a planar chiral ferrocene moiety linked to hydroxyl-imine or diimine donors with central or axial chirality. Structurally, these ligands resemble half-salen and salen systems designed for stereoselective applications of their transition metal complexes in homogeneous catalysis. The modular synthesis involves diastereoselective metalation of chiral ferrocene or pentamethylferrocene acetals, followed by stereoconservative hydroxyalkylation and condensation with chiral hydroxyamines or diamines, respectively. In comparison to salen-type systems, an important advantage of these ligands is their tunable steric protection of the alkoxide donor site. A total of 18 different ligands varying in electronic and steric properties have been prepared and fully characterized by NMR, IR, mass spectroscopy and by single crystal structure analysis of nine precursors and representatives.

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Chiral 2 + 3 Keto-Enamine Pseudocyclophanes Derived from 1,3,5-Triformylphloroglucinol

The reactions of 1,3,5-triformylphloroglucinol with (1R,2R)-1,2-diaminocyclohexane, (1R,2R)-1,2-diphenylethylenediamine, or (R)-2,2′-diamino-1,1′-binaphthyl result in the formation of enantiopure [2 + 3] keto-enamine condensation products, in contrast to analogous reactions of 1,3,5-triformylbenzene, where [4 + 6] Schiff base cages are formed. The X-ray crystal structure of the diaminocyclohexane 2 + 3 derivative as well as modeled structures of other compounds of this type show cyclophane-like molecules with close contact between the phloroglucinol rings. Density Functional Theory (DFT) calculations confirm that there is a sizable pi-pi interaction between these rings influencing the conformation of these molecules.

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Mechanism of living lactide polymerization by dinuclear indium catalysts and its impact on isoselectivity

A family of racemic and enantiopure indium complexes 1-11 bearing bulky chiral diaminoaryloxy ligands, H(NNOR), were synthesized and fully characterized. Investigation of both the mono- and the bis-alkoxy-bridged complexes [(NNOR)InX]2[mu-Y][mu-OEt] (5, R = tBu, X = Y = Cl; 8, R = Me, X = I, Y = OEt) by variable temperature, 2D NOESY, and PGSE NMR spectroscopy confirmed dinuclear structures in solution analogous to those obtained by single-crystal X-ray crystallography. The dinuclear complexes in the family were highly active catalysts for the ring-opening polymerization (ROP) of lactide (LA) to form poly(lactic acid) (PLA) at room temperature. In particular, complex 5 showed living polymerization behavior over a large molecular weight range. A detailed investigation of catalyst stereoselectivity showed that, although (R,R/R,R)-5 is highly selective for l-LA, only atactic PLA is obtained in the polymerization of racemic LA. No such selectivity was observed for complex 8. Importantly, the selectivities obtained for the ROP of racemic LA with (R,R/R,R)-5 and (R,R/R,R)-8 are different and, along with kinetics investigations, suggest a dinuclear propagating species for these complexes.

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Ar-BINMOL-derived salan-Cu(II) complex-catalyzed silyl-reformatsky reaction of aromatic aldehydes

In this work, we have developed a facile protocol with salan-Cu system for the facile and selective synthesis of beta-hydroxyesters via silyl-Reformatsky reaction with -silylester and aldehydes. The screening and optimization of reaction conditions led to the determination of a practical and efficient procedure in which the salan-Cu exhibited promising catalytic activity in dimethylsulfoxide, in which the silyl-Reformatsky reaction of aromatic aldehydes with -trimethylsilylmethylacetate gave the corresponding beta-hydroxyester derivatives in excellent yields (up to 98%) under fluoride-free reaction conditions.

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From Concept to Crystals via Prediction: Multi-Component Organic Cage Pots by Social Self-Sorting

We describe the a priori computational prediction and realization of multi-component cage pots, starting with molecular predictions based on candidate precursors through to crystal structure prediction and synthesis using robotic screening. The molecules were formed by the social self-sorting of a tri-topic aldehyde with both a tri-topic amine and di-topic amine, without using orthogonal reactivity or precursors of the same topicity. Crystal structure prediction suggested a rich polymorphic landscape, where there was an overall preference for chiral recognition to form heterochiral rather than homochiral packings, with heterochiral pairs being more likely to pack window-to-window to form two-component capsules. These crystal packing preferences were then observed in experimental crystal structures.

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COMPOUNDS

Compounds of formula (I): are useful as inhibitors of human neutrophil elastase.

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Synthesis and x-ray crystallography of chiral tropocoronands

The synthesis of several chiral tropocoronands (6 and 7) has been accomplished. These compounds have been shown to complex with various metals. Tropocoronands that have been synthesized include H2(TC-3,cyhex) through H2(TC-6,cyhex) (6) and H2 (TC-3,diphen) through H2(TC-6,diphen) (7). The route is short and the tropocoronands are easily purified by chromatography or recrystallization. Two other groups have been incorporated into tropocoronands, H2(TC-3,binap) (9) and H2(TC-6,pent) (10).

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Functionalization of indole at C-5 or C-7 via palladium-catalysed double carbonylation. A facile synthesis of indole ketocarboxamides and carboxamide dimers

Palladium-catalysed aminocarbonylation of 7-iodoindole derivatives (the parent compound and 5-bromo-7-iodoindole), as well as 5-iodoindole with various primary and secondary amines, including amino acid esters and chiral diamines, was carried out. In this way, a highly selective double carbonylation reaction at the C-7 was performed resulting in the formation of the corresponding indol-7-ylglyoxylamides when monoamines were used. The bromoarene moiety remained intact, so bromo-substituted glyoxylamides of practical importance have been synthesised in moderate to high yields. The use of chiral alkyl and aryl diamines as nucheophiles allowed the synthesis of a new family of dimeric 7-indole derivatives under moderate reaction conditions (10 bar, 100 C). The aminocarbonylation at the C-5 position led to much lower chemoselectivities toward indol-5-ylglyoxylamides under similar conditions (40 bar CO, 50 C). The aminocarbonylation of iodoindoles shows a strikingly different chemoselectivity depending on the basicity of the amine while primary and secondary amines of high basicity gave 2-ketocarboxamides in up to 98% chemoselectivity, aniline resulted in almost exclusive formation of the corresponding carboxamide product.

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Catalytic asymmetric synthesis of trans-configured beta-lactones: Cooperation of Lewis acid and ion pair catalysis

The development of the first trans-selective catalytic asymmetric [2+2] cyclocondensation of acyl halides with aliphatic aldehydes furnishing 3,4-disubstituted beta-lactones is described. This work made use of a new strategy within the context of asymmetric dual activation catalysis: it combines the concepts of Lewis acid and organic aprotic ion pair catalysis in a single catalyst system. The methodology could also be applied to aromatic aldehydes and offers broad applicability (29 examples). The utility was further demonstrated by nucleophilic ringopening reactions that provide highly enantiomerically enriched anti-aldol products.

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