Ryszard Bodalski

Horner-Wadsworth-Emmons olefination of nonstabilized phosphonates. A new synthetic approach to β,γ-unsaturated amides

Abstract Aminolysis of readily accessible β-diethoxyphosphonyl-γ-butyrolactones 5 and 22 provides a convenient entry to (E)-β,γ-unsaturated amides 8 and 24 respectively. The key step of the aminolysis involves elimination of diethoxyphosporic acid from the corresponding β-hydroxyalkylphosphonates 7 and 23. Stereochemistry of the amides 8 and 24 results from their consecutive base catalyzed isomerization.

SYNTHESIS OF OPTICALLY ACTIVE 4-OXO-1-PHENYL-2-PHOSPHOLENE-1-OXIDE AND THE DETERMINATION OF ITS CONFIGURATION

Abstract (+)-(1S,4R)-4-hydroxy-1-phenyl-2-phospholene-1-oxide (+)-(4a) was obtained by optical resolution of the corresponding ω-camphanates 5a and converted into (+)-(S)-4-oxo-1-phenyl-2-phospholene-1-oxide (+)-(1a). The absolute stereochemistry of (+)-(4a) was determined by a single-crystal X-ray analysis.

β-Diethoxyphosphorylpropionic acid, a convenient reagent for the synthesis of β,δ - unsaturated amides

Abstract β-Diethoxyphosphorylpropionic acid (1) is converted into δ-substituted β-(diethoxyphosphoryl)-δ-lactones 5 by LDA promoted reaction with carbonyl compounds 3. Aminolysis or alternatively a standard alkylation and aminolysis of 5 afford (E)- β,δ-unsaturated amides 7 or 10 in good yield.

SYNTHESIS AND ABSOLUTE CONFIGURATION OF DIASTEREOMERIC MENTHYL BENZYLPHOSPHINATES

Abstract Diastereomerically pure Rp-menthyl benzylphosphinate (7a) and diastereomerically enriched Sp-menthyl benzylphosphinate (7b) have been prepared and their absolute configurations have been corroborated via chemical correlation.

Studies with Metaphosphoric Acid Derivatives

Abstract A variety of O-alkyl, N.N-dialkylamino, and N-alkylamino metaphosphates, as well as O-alkyl metathiophosphates, have been generated by thermal or photochemical fragmentation of 2,3- axaphosphabicyclo[2.2.2]octene derivatives. The metaphosphoric acid derivatives are detected by trapping reactions, including a new reaction with epaxides to form 1,3,2-diaxaphospholanes, and by direct 31P NMR observation on THF solutions at -78°C. Applications of metaphosphates as novel phosphorylating agents are possible.

The molecular and crystal structure of endo-2-methyl-7-hydroxy-7-oxo-N-phenyl-7-phosphabicyclo-[2.2.1] hept-2-ene-5,6-dicarboximide

The structure of the title compound1 has been determined by X-ray crystallography analysis. The following crystal data were found: orthorhombic,Pca2l,a=9.60691),b=16.356(1),c=8.686(1) Å. Both the phospholane and phospholene rings involved in the 7-phosphabicyclo-[2.2.1] hept-2-ene system have almost regular envelope conformations, and the cyclohexene ring has a significantly deformed boat conformation. The low value of the C−P−C angle, 84.2(2)°, reflects the steric strain around the phosphorus bridge and may be responsible for the reactivity of esters and amides derived from1 in the O-insertion reaction with m-chloro-perbenzoic acid. The dihedral angle between the plane of the benzene and succinimide rings is 82.4(2)°.

Crystal structure of 7-cyano-6,7-dimethyl-1-phenyl-1,3,6,7-tetrahydro-2,1-benzoxaphospole 1-oxide

The crystals (C16H18NO2P,Mr=287.30) are orthorhombic, space group Pbca witha=8.200(2),b=14.857(2), andc=24.396(5)Å,V=2972.1 Å3,Z=8,Dx=1.284 mg m−3,λ(MoKα)=0.71069 Å,μ=1.90 cm−1,F(000)=216,T=295K. FinalR=0.044 for 1673 observed reflections collected on a diffractometer. Structure solved by direct methods.Cis-junction and double bond in the six-membered ring cause its almost ideal sofa conformation. The two neighboring methyl groups are cis, and cyano substituent is in an equatorial position. There is a shortintramolecular H(o-phenyl)⋯O(endocyclic) contact of 2.53(3)Å and the phenyl ring is in a less favorable rotational orientation due to molecular packing.