M. N. Dimukhametov

The Molecular Design of “Carcass”-Type Phosphoranes, Based on the Reaction of P(III)-Cyclic Derivatives and Unsaturated Activated Compounds

Abstract The methodology for the synthesis of carcass-type (cage-like type) phosphoranes was developed, which allows us to obtain the products of the given structure with a high regio- and stereoselectivity in the result of cascade processes.

A New Approach to The Synthesis of Phosphoranes Based on the Reaction of Benzo[d]-1,3,2-Dioxaphospholes, Having β- or γ-Unsaturated Group in a Substituent, with Compounds Containing Multiple Bonds

We developed a new approach to the synthesis of phosphoranes and carba phosphatranes on the basis of the reaction of benzo[d]-1,3,2-dioxaphospholes, having β- or γ-unsaturated group in a substituent, with such compounds containing multiple bonds, such as hexafluoroacetone, chloral, and diethylacetylenedicarboxylate.

Synthesis and steric structure of 3′,3′,5′-trimethyl-7′,7′-bis(trifluoromethyl)spiro[1,3,2-benzodioxaphosphole-2,1′-[2,6,8]trioxa[1λ5]phosphabicyclo[3.2.1]octane] and 3′,5′-dimethyl-7′,7′-bis(trifluoromethyl)spiro[1,3,2-benzodioxaphosphole-2,1′-[2,6,8]trioxa[1λ5]phosphabicyclo[3.2.1]oct[3]ene]

Reactions of hexafluoroacetone with 4-(1,3,2-benzodioxaphosphol-2-yloxy)-4-methylpentan-2-one and 4-(1,3,2-benzodioxaphosphol-2-yloxy)pent-3-en-2-one afforded cage spiro phosphoranes with a phosphorus-carbon bond, 3′,3′,5′-trimethyl-7′,7′-bis(trifluoromethyl)spiro[1,3,2-benzodioxaphosphole-2,1′-[2,6,8]-trioxa[1λ5]phosphabicyclo[3.2.1]octane] and 3′,5′-dimethyl-7′,7′-bis(trifluoromethyl)spiro[1,3,2-benzodioxaphosphole-2,1′-[2,6,8]trioxa[1λ5]phosphabicyclo[3.2.1]oct[3]ene], whose structure was determined by X-ray analysis.

Formation of the cage-like phosphoranes with the P-C and P-N bonds in the reactions of 2-(2-benzylidenamino)phenoxy-4- tert -butylbenzo-1,3,2-dioxaphosphol with ethyl mesoxalate and ethyl trifluoropyruvate

The reaction of 2-(2-benzylidenamino)phenoxy-4-tert-butylbenzo-1,3,2-dioxaphosphol with ethyl mesoxalate and ethyl trifluoropyruvate resulted in the formation of tricyclic phosphoranes with the P-C and P-N bonds. The adduct emerged from the initial reaction of the PIII derivative with the activated ketone (1: 1), further underwent the transformation via the intramolecular reaction involving the benzylideniminoaryl substituent, which resulted in the formation of the cage-like phosphoranes.

Caged phosphorane with P-C bond based on chloral and 4,5-dimethyl-2-(2-oxo-1,2-diphenylethoxy)-1,3,2-dioxaphospholane

The key methods of caged phosphoranes synthesis are analyzed. Reaction of 4,5-dimethyl-2-(2-oxo-1,2-diphenylethoxy)-1,3,2-dioxaphospholane (prepared from the meso-form of 2,3-butanediol) with chloral has yielded the caged phosphorane containing a phosphorus-carbon bond: 1,1-(1,2-dimethylethylenedioxy)-3,4-diphenyl-6-trichloromethyl-2,5,7,1-trioxaphosphabicyclo[2.2.11,4]heptane; spatial structure of the product has been elucidated with X-ray diffraction analysis.

Caged C-P phosphoranes based on 2-(2-methyl-4-oxopent-2-yloxy)- and 2-[2-(methylcarbonyl)-1-phenoxy]-1,3,2-benzodioxaphospholes and diethyl mesoxalate

Cascade reactions of 2-(2-methyl-4-oxopent-2-yloxy)- and 2-[2-(methylcarbonyl)-1-phenoxy]-1,3,2-benzodioxaphospholes with diethyl mesoxalate yield caged phosphoranes containing a phosphoruscarbon bond: 7,7-bis(ethoxycarbonyl)-3,3,5-trimethyl-1,1-phenylenedioxy- and 7,7-bis(ethoxycarbonyl)-5-methyl-1,1-phenylenedioxy-3,4-benzo-2,6,8,1λ5-trioxaphosphabicyclo[3.2.11.5]octanes. Spatial structure of latter product has been determined by X-ray diffraction analysis.

Stereoselective PCO/POC-Rearrangement of P-C-Cage Phosphorane in the Reaction of 4,5-Dimethyl-2-(2-oxo-1,2-diphenyl)ethoxy-1,3,2-dioxaphospholane with Hexafluoroacetone.

Interaction of 4,5-dimethyl-2-(2-oxo-1,2-diphenyl)ethoxy-1,3,2-dioxaphospholane, bearing a carboxyl group in the γ-position with respect to the phosphorus atom and obtained from d,l-butanediol, with hexafluoroacetone (CCl4, -40 °C) leads to the simultaneous formation of regio- and stereoisomeric cage-like phosphoranes with phosphorus-carbon and phosphorus-oxygen bonds with a high stereoselectivity (>95%), whose structure was determined by 1D and 2D NMR spectroscopy and XRD. When stored as a solution in dichloromethane for one month, the PCO-isomer rearranges into the thermodynamically more stable POC-isomer of the cage-like phosphorane. Mild hydrolysis of the PCO/POC-isomers proceeds with a high chemoselectivity and leads to the formation of P(IV)-dioxaphospholane derivatives. Acidic hydrolysis of the POC-isomer leads to the formation of an oxirane derivative with an unexpectedly high stereoselectivity (>95%). DFT calculations (using the PBE functional) allowed us to obtain structures and energies of the initial phospholane, reaction products (PCO/POC-isomers), and an intermediate P(V)-oxaphosphirane.

A New Approach to the Synthesis of Spirophosphoranes on the Basis of Spontaneous Rearrangement of O,O′-Bis(2-Iminophenyl) Arylphosphonites

Abstract O,O-bis(2-benzylideneaminophenyl) arylphosphonites undergo a spontaneous rearrangement into spirophosphoranes, 1-aryl-6,7-diphenyl-3,4:9,10-dibenzo-2,11-dioxa-5,8-diaza-1-phosphatricyclo[6.3.0.01,5]undeca-3,9-dienes. GRAPHICAL ABSTRACT

Synthesis and Structure of Tris(halo)alkyl Phosphate Complexes with Metal Chlorides

Complexes were prepared of some orthophosphoric acid esters with metal chlorides. The composition and structure of complexes synthesized were investigated by IR, 1H and 31P NMR, mass spectroscopy, and XRD analysis.

Reactions of 2-(2-Arylidenaminoaryloxy)Areno-1,3,2-Dioxaphosphole with Trifluoropyruvic and Mesoxalic Ethyl Esters. Synthesis of Cage Phosphoranes with the P–C and P–N Bonds

GRAPHICAL ABSTRACT Abstract Reaction of 2-(2-arylidenaminoaryloxy)areno-1,3,2-dioxaphosphole with trifluoropruvic and mesoxalic ethyl esters gives tricyclic cage phosphoranes with the P–C and Р–N bonds. The structure of one isolated diastereoisomer was established by XRD.