Igor S. Mikhel

QUININE-BASED DIOXAPHOSPHOLANE WITH N-DECYLQUINUCLIDINE FRAGMENT

Abstract The ionic organophosphorus compound 2 with dioxaphospholane cycle, N-decylquininium bromide 1 derivative, was obtained for the first time. Its structures is discussed on the basis of 31P and 13C NMR IR, XPS, plasma desorption mass spectrometry and ultracentrifugation data.

Chiral amido- and diamidophosphites with a peripheral pyridine ring in Pd-catalyzed asymmetric allylation

New chiral amidophosphite and diamidophosphite ligands with exocyclic pyridyl-containing substituents were obtained. Their efficiency in the Pd-catalyzed enantioselective allylic substitution was compared: in the sulfonylation of (E)-1,3-diphenylallyl acetate with sodium p-toluenesulfinate, the ee can reach 77%; its alkylation with dimethyl malonate and amination with pyrrolidine gave up to 80% and 74% ee, respectively. The asymmetric alkylation of cinnamyl acetate with ethyl 2-oxocyclohexanecarboxylate can provide to 68% ee. The complexation of zinc(ii) 5,10,15,20-tetraphenylporphyrinate with diamidophosphite ligand and its influence on conversion and enantioselectivity of the process were studied.

Platinum and rhodium complexes with isoleucinol-based bi- and tricyclic hydrophosphoranes

The complex formation of bi- and tricyclic hydrophosphorane derivatives of isoleucinol with [Pt(COD)Cl2], [Rh(CO)2Cl]2, and [Rh(THF)2(COD)]+BF4– (COD is cycloocta-1,5-diene) was investigated. In all cases, bicyclic hydrospirophosphorane selectively forms the metal chelates [M(η2-P∩N)(X)Cl] (M = Pt, X = Cl; M = Rh, X = CO) and [Rh(η2-P∩N)(COD)]+BF4–. («∩» denotes the residue of the hydrospirophosphorane ligand, which does not contain the P and N atoms). In addition, tricyclic hydrophosphorane (L) generates the phosphoranide complexes [Pt(η1-L)(COD)Cl]+Y– (Y = Cl or BF4). The structures of the new compounds were established by IR spectroscopy, 31P, 13C, 1H, 2H, 11B, 19F, and 195Pt NMR spectroscopy, and plasma-desorption and electrospray ionization mass spectrometry. The possible mechanism of coordination of hydrophosphoranes is discussed.

The first example of coordination of a tricyclic hydrophosphorane with platinum(II)

aN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp.. 117913 Moscow, Russian Federation. fax: 007 (095) 135 5328 bS. A. Esenin Ryazan State University of Education, 46 ul. Svobody, 390000 Ryazan, Russian Federation. Fax: 007 (091 2) 44 4390. E-maih chem@ttc.ryazan.ru CA. K Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninsky prosp., 117912 Moscow, Russian Federation. Fax: 007 (095) 23

First ligand of phosphite nature based on 5,10,15,20-tetrakis(4-hydroxyphenyl)porphin

Supramolecular asymmetric catalytic systems are formed involving chiral phosphites and amidophosphites underlain by metalloporphyrins [9–15], yet only one chiral phosphite has been prepared with a porphyrin fragment without a metal ion [9]. No published information exists on diamidophosphite porphyrin derivatives, in particular, with asymmetric phosphorus atoms, and also on compounds containing in their composition more than one phosphorus site linked to the porphyrin scaffold.

Asymmetric Ir-catalyzed hydrogenation of 1,3-dihydro-2 H -1,5-benzodiazepin-2-ones using phosphoramidites

A series of phosphoramidite ligands was tested in the asymmetric hydrogenation of 4-arylsubstituted 1,3-dihydro-2H-benzodiazepine-2-ones and up to 52% ee was achieved. The effects of various factors (solvents, hydrogen pressure, and addition of phosphine ligands) on the hydrogenation were studied.

An alliance between chiral phosphite-type compounds and porphyrins in asymmetric palladium catalysis

GRAPHICAL ABSTRACT ABSTRACT Some novel results obtained at the confluence of organophosphorus and porphyrin chemistry are briefly overviewed. The focus is put on the P*-chiral porphyrin-appended diamidophosphite ligands as well as achiral metalloporphyrins used in Pd-catalyzed asymmetric allylation.