ABSTRACT
A new hemicryptophane host with a ditopic molecular cavity combining a cyclotriveratrylene (CTV) unit with a tris-urea moiety was synthesized. The complexation of halides, tetramethylammonium (TMA+) cation, and ion pairs was investigated. A positive cooperativity was observed, since halides display a higher binding constant when a TMA+ cation is already present inside the cage. When TMA+ was complexed alone, a decrease of temperature from 298â K to 230â K was required to switch from a fast to a slow exchange regime on the NMR time scale. Nevertheless, the prior complexation of a halide guest in the lower part of the host resulted in significant decrease of the exchange rate of the subsequent complexation of the TMA+ cation. Under these conditions, the 1H NMR signals characteristic of a slow exchange regime were observed at 298â K. Addition of an excess of salts, increases the ionic strength of the solution, restoring the fast exchange dynamics. This result provides insight on how the exchange rate of a cation guest can be modulated by the complexation of a co-guest anion.
ABSTRACT
Accessing each enantiomer of a chiral molecule starting from a racemic mixture remains a daunting challenge in chemistry. Indeed, until now, only a few solutions exist to separate enantiomers of an equimolar mixture of a chiral precursor. In this study, we establish a new strategy to prepare simultaneously and physically separate both enantioenriched enantiomers of a molecule starting from a racemic substrate. This process combines two enantiomeric catalytic systems, working in parallel, and separation by an achiral membrane with selective permeability. This unprecedented system was successfully applied to the simultaneous preparation of both enantiomers of chiral 1,2-diols starting from racemic epoxides using Jacobsen's hydrolytic kinetic resolution (HKR) in parallel.
ABSTRACT
A highly selective recognition of fluoride was achieved through the design of a small hemicryptophane cage (3) presenting a southern tris-urea hosting moiety. The resulting host-guest complex has been characterized by electrospray ionization-high-resolution mass spectrometry, 1H and 19F NMR, and X-ray diffraction techniques. In particular, X-ray diffraction analysis of [3·F-] reveals that the encapsulation of one fluoride, within 3, occurs through NH···F- H-bonding with the six NH residues of the tris-urea ligand. An association constant of 1200 M-1 was extracted from 1H NMR titration experiments, indicating that efficient fluoride binding also occurs in solution. Finally, in sharp contrast with previously reported urea-based hemicryptophane hosts, the small preorganized cavity found in 3 allows for an exclusive selectivity for fluoride over other competing halides.
ABSTRACT
We disclosed therein a new reaction of reductive isomerization of methylenecyclopropanes (MCPs) to vinylcyclopropanes (VCPs). On treatment with sodium metal in liquid ammonia, MCPs bearing a C-O bond at allylic position undergo both a reductive cleavage of the C-O bond and an isomerization of the C-C double bond giving rise to VCPs. The scope of the reductive isomerization was investigated and showed a broad applicability since various functional groups are tolerated. MCP substrates were straightforwardly prepared by a palladium-promoted [2 + 1] cycloaddition between norbornene derivatives with alkynes.
ABSTRACT
We synthesized a series of biomimetic self-assembling phthalocyanines equipped with carbonyl groups as recognition motifs, a central zinc atom and diverse solubilizing alkyl chains mimicking for the first time with these robust pigments the natural chlorosomal bacteriochlorophylls. Upon self-assembly a very broad and red-shifted Q-band absorption extending to over 900 nm is put into evidence.
