1159633-63-2

Upstream product

• 88123-43-7 (E,E)-1,4-dideutero-1,4-diphenyl-1,3-butadiene 
• 886-65-7 trans,trans-1,4-Diphenyl-1,3-butadiene 
• 1159633-62-1 (1s,2R,5S)-1-(diethylamino)-2,5-diphenyl-2,5-dihydro-1H-phosphole 1-oxide 

Downstream Products

• 1159633-65-4 (5R)-1-hydroxy-1-oxo-2,5-diphenyl-4,5-dihydro-1H-phosphole 
• 226393-33-5 (R,R)-(+)-1-hydroxy-1-oxo-2,5-trans-diphenylphospholane 
• 287733-60-2 1-hydroxy-cis-2,5-diphenyl-1λ⁵-phospholan-1-one 
• 1428255-91-7 (2R,5R)-1-diethylamino-1-oxo-2,5-diphenylphospholane 
• 474049-73-5 (S,S)-(-)-1-hydroxy-1-oxo-2,5-trans-diphenylphospholane 

Relevant academic research and scientific papers

Enantioselective synthesis of phospholenes via asymmetric organocatalytic alkene isomerization

An asymmetric synthesis of the 2,5-diphenylphosphol-2-ene fragment (≥95% ee) has been realized via enantioselective Cinchona-alkaloid catalyzed double bond isomerization of a meso-2,5-diphenylphosphol-3-ene amide to a 2,5-diphenylphosphol-2-ene amide (up to 83% ee), followed by enantiomeric enrichment to ≥95% ee by crystallization. The 2,5-diphenylphosphol-2-ene amide (a cyclic phosphinic acid amide) was hydrolyzed to the 2,5-diphenylphosphol-2-ene acid (a cyclic phosphinic acid) with retention of configuration at C-5.

Organocatalytic stereoisomerization versus alkene isomerization: Catalytic asymmetric synthesis of 1-hydroxy-trans -2,5-diphenylphospholane 1-oxide

The potential for an organocatalytic asymmetric stereoisomerization or alkene isomerization as atom-economic reaction with minimal structural change was investigated. The McCormack cycloaddition of 1,4-diarylbuta-1,3-dienes with (dialkylamino)dichlorophosphane and aluminum trichloride gives meso-2,5-diaryl-1-(dialkylamino)-1-oxo-2,5-dihydro-1H-phospholes, which were identified as suitable substrates for asymmetric isomerization to (1R,5R)-2,5-diaryl-1-(dialkylamino)-1-oxo-4,5-dihydro-1H-phospholes in the presence of bifunctional organocatalysts (cinchona alkaloids, Takemoto catalyst) in up to 91% ee and quantitative yield. The substrate range and the mechanism of the catalysis were studied. The reaction involves proton abstraction by the base, but a primary deuterium KIE is absent. Enriched (1R,5R)-1-(diethylamino)- 1-oxo-2,5-diphenyl-4,5-dihydro-1H-phosphole was hydrolyzed to (5R)-1-hydroxy-1-oxo-2,5-diphenyl-4,5-dihydro-1H-phosphole, which was hydrogenated diastereoselectively under dissolving metal conditions to give (2R,5R)-1-hydroxy-1-oxo-2,5-diphenylphospholane (Fiaud's acid) in preference to meso-1-hydroxy-1-oxo-2,5-diphenylphospholane. An asymmetric catalytic total synthesis of Fiaud's acid, which is a building block for chiral phospholane synthesis, has been realized in five steps from thiophene, using nickel-catalyzed Wenkert arylation, McCormack cycloaddition, asymmetric dihydro-1H-phosphole isomerization, hydrolysis, and diastereo-selective hydrogenation. Georg Thieme Verlag Stuttgart New York.