Manganese(I)-Catalyzed Enantioselective Formal Anti-Markovnikov Hydroalkoxylation of Racemic Allylic Alcohols: A Borrowing Hydrogen Access.

An enantioselective manganese(I)-catalyzed formal anti-Markovnikov hydroalkoxylation of racemic allylic alcohols has been developed using a chiral N-type macrocyclic ligand, affording a wide range of chiral γ-alkoxypropyl alcohols in high isolated yields with excellent enantioselectivities. The synthetic utility of this protocol was further proven by gram-scale synthesis of chiral γ-alkoxypropanol and derivatization of chiral γ-alkoxypropanol to a drug molecule, ()-dapoxetine, for the treatment of premature ejaculation and erectile dysfunction. Mechanistic studies support that the reaction proceeds via a hydrogen-borrowing cascade reaction pathway.

Manganese-Catalyzed Asymmetric Formal Hydroamination of Allylic Alcohols: A Remarkable Macrocyclic Ligand Effect.

A unique family of chiral peraza N -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 Mn complex indicates that the manganese atom coordinates with the chiral dialkylamine moiety in a bidentate fashion.

[Study on the immunophenotypes of bone marrow cells from patients with myelodysplastic syndromes and its clinical implications].

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.