RESUMO
A unique family of chiral peraza N6 -macrocyclic ligands, which are conformationally rigid and have a tunable saddle-shaped cavity, is described. Utilizing their manganese(I) complexes, the first example of earth-abundant transition metal-catalyzed asymmetric formal anti-Markovnikov hydroamination of allylic alcohols was realized, providing a practical access to synthetically important chiral γ-amino alcohols in excellent yields and enantioselectivities (up to 99 % yield and 98 % ee). The single-crystal structure of a MnI complex indicates that the manganese atom coordinates with the chiral dialkylamine moiety in a bidentate fashion. Further DFT calculations revealed that five of the six nitrogen atoms in the ligand were engaged in multiple noncovalent interactions with Mn, an isopropanol molecule, and a ß-amino ketone intermediate via coordination, hydrogen bonding, and/or CHâ â â π interactions in the transition state, showing a remarkable role of the macrocyclic framework.
RESUMO
The phenotypes of the bone marrow cells in various subtypes of myelodysplastic syndromes (MDS) and its clinical implication were explored. The antigen expression of a panel of antigens expressed in marrow cells from 30 patients with subtypes of MDS was assayed by alkaline phosphatase anti-alkaline phosphatase method. The results showed that the expression of myeloid antigens appeared abnormality, CD13 and CD33, found on granulocyte and macrophage precursors, increased, and CD15 decreased. There were no significant changes for monocytic antigen CD14 and lymphoid antigens CD7 and CD10. CD34 was increased in RAEB/RAEB-t and was not increased in RA/RAS patients. CD71, expressed by erythroblast and proliferative cells, was higher in all subtypes of MDS than that in control group. It is suggested that the bone marrow cells from MDS patients showed abnormality of more than two series of immunophenotypes, detection of immunophenotype in MDS cells might be contributed to the diagnosis and predicting prognosis.