Bifunctionalized Allenes. Part XVI. Synthesis of 3-Phosphoryl-2,5-dihydrofurans by Coinage Metal-Catalyzed Cyclo-isomerization of Phosphorylated α-Hydroxyallenes.

Phosphorylated α-hydroxyallenes 1 and 2 were smoothly converted into the corresponding 2,5-dihydrofurans 3 and 4 in an 5-endo-trig cycloisomerization reaction by using 5 mol % of coinage metal salts as catalyst. Experimental conditions such as the type of the solvent, the reaction temperature, the mol % and the type of the catalyst were optimized. This mild and efficient cyclization method can be applied to dimethyl 1-hydroxyalkyl-alka-1,2-dienephosphonates 1 and 2-diphenylphosphinoyl-2,3-dien-1-ols 2a-c and 3-diphenylphosphinoyl-3,4-dien-2-ols 2d,e, furnishing 3-phosphorylated 2,5-dihydrofurans 3 and 4 in very good yields.

Bifunctionalized allenes. Part XV. Synthesis of 2,5-dihydro-1,2-oxaphospholes by electrophilic cyclization reaction of phosphorylated α-hydroxyallenes.

This paper discusses a reaction of phosphorylated α-hydroxyallenes with protected or unprotected hydroxy groups involving 5-endo-trig cyclizations. Various electrophilic reagents such as sulfuryl chloride, bromine, benzenesulfenyl and benzeneselenenyl chlorides have been applied. The paper describes the reaction of 1-hydroxyalkyl-1,2-dienephosphonates with electrophiles that produces 2-methoxy-2-oxo-2,5-dihydro-1,2-oxaphospholes due to the participation of the phosphonate neighbouring group in the cyclization.

Bifunctionalized allenes. Part XIII. A convenient and efficient method for regioselective synthesis of phosphorylated α-hydroxyallenes with protected and unprotected hydroxy group.

The paper describes a convenient and efficient method for regioselective synthesis of phosphorylated α-hydroxyallenes using an atom economical [2,3]-sigmatropic rearrangement of intermediate propargyl phosphites or phosphinites. These can be readily prepared via reaction of protected alkynols with dimethyl chlorophosphite or chlorodiphenyl phosphine respectively in the presence of a base.

Endoscopically directed external support of femoral vein valves.

Background: This study investigated the optimization of indications to external valve support using the Vedensky Spiral for primary deep venous reflux based on the femoral vein proximal (ostial) valve anatomy type.

Methods: The external Vedensky Spiral was used for correction of valvular insufficiency in 28 extremities of 24 patients (18 women, 6 men) during 1998 to 2002. Patients were a mean age of 54.