Immobilized box-Cu complexes are able to efficiently catalyze the insertion of a carbene, from methyl phenyldiazoacetate, into C-H bonds of THF, with high enantioselectivity (up to 88% ee). The immobilization not only allows recovery and reuse of the enantioselective catalyst but also provides an improvement in the selectivities from the values obtained in solution, probably due to a confinement effect of the bidimensional support. [reaction: see text].

123 Genet Resour Crop Evol (2011) 58:125-137 DOI 10.1007/s10722 -010-9601-5 currently consists of 220 accessions from 15 countries: 169 of these come from European cultivation countries, 18 from commercial areas in non EU countries, 26 from regions of minimal or relict production and/or from abandoned fields and 7 from commercial nurseries. The non-saffron Crocus collection currently comprises 352 accessions: 179 collected from the wild in 12 countries of natural distribution, 24 from donations of public and private institutions, 91 from commercial nurseries and 58 acquired from BGV-CU collection management. Here we provide a record of collections, activities concerns and current strategies for documentation, conservation, characterisation, and management of the collection as important tools for researchers with interest in these valuable genetic resources.

The presence and extent of genetic variation in saffron crocus are still debated, as testified by several contradictory articles providing contrasting results about the monomorphism or less of the species. Remarkably, phenotypic variations have been frequently observed in the field, such variations are usually unstable and can change from one growing season to another. Considering that gene expression can be influenced both by genetic and epigenetic changes, epigenetics could be a plausible cause of the alternative phenotypes. In order to obtain new insights into this issue, we carried out a molecular marker analysis of 112 accessions from the World Saffron and Crocus Collection. The accessions were grown for at least three years in the same open field conditions. The same samples were analysed using Amplified Fragment Length Polymorphism (AFLP) and Methyl Sensitive AFLP in order to search for variation at the genetic (DNA sequence) and epigenetic (cytosine methylation) level. While the genetic variability was low (4.23% polymorphic peaks and twelve (12) effective different genotypes), the methyl sensitive analysis showed the presence of high epigenetic variability (33.57% polymorphic peaks and twenty eight (28) different effective epigenotypes). The pattern obtained by Factorial Correspondence Analysis of AFLP and, in particular, of MS-AFLP data was consistent with the geographical provenance of the accessions. Very interestingly, by focusing on Spanish accessions, it was observed that the distribution of the accessions in the Factorial Correspondence Analysis is not random but tends to reflect the geographical origin. Two clearly defined clusters grouping accessions from the West (Toledo and Ciudad Real) and accessions from the East (Cuenca and Teruel) were clearly recognised.

A thorough experimental and theoretical study of the enantioselective cyclopropanation of alkenes catalyzed by chiral bis(oxazoline)- and azabis(oxazoline)-copper complexes, which comprise a new family of ligands that lack C2 symmetry, has been conducted. Surprisingly high enantioselectivities were observed with some of these ligands, which were rationalized on the basis of molecular modeling studies. The course of the asymmetric induction in connection with ligand symmetry and the implications for supported enantioselective catalysts are discussed.