474093-56-6

Upstream product

• 226393-36-8 1-(N,N-dimethylamino)-1-r-oxo-2-t,5-t-diphenylphospholane 
• 226393-31-3 1-(N,N-dimethylamino)-1-r-oxo-2-t,5-t-diphenylphosphol-3-ene 
• 886-65-7 trans,trans-1,4-Diphenyl-1,3-butadiene 
• 474049-73-5 (S,S)-(-)-1-hydroxy-1-oxo-2,5-trans-diphenylphospholane 

Downstream Products

• 474093-54-4 (2S,5S)-(-)-1-r-oxo-1,2-c,5-triphenyl phospholane 
• 949575-86-4 (2S,5S)-(-)-1-(6-tert-butoxypyrid-2-yl)-1-oxo-2,5-diphenylphospholane 
• 949575-78-4 (2S,5S)-(+)-6-(tert-butoxypyrid-2-yl)-2,5-diphenylphospholane 

Relevant academic research and scientific papers

Efficient enantiodiscrimination of chiral monophosphine oxides and boranes by phosphorus coupled 13C NMR spectroscopy in the presence of chiral ordering agents

The synthesis of new chiral phospholanes via the corresponding oxides or boranes is reported and the analytical potential of 13C-{1H} NMR spectroscopy in weakly ordering polypeptide liquid crystalline phases in view to differentiate between enantiomers of these chiral phosphines precursors is explored. In particular results involving organic solutions of poly-γ-benzyl-L-glutamate (PBLG) and poly-ε-carbobenzyloxy-L-lysine (PCBLL) are described. This NMR approach allows determination of the enantiomeric composition, and provides therefore a new efficient alternative to classical methods usually used to analyze this class of compounds. A description of various spectral enantiodifferentiation patterns expected to be observed using 13C-{1H} NMR of enantiomers having a spin-1/2 heteroatomic nucleus, embedded in a chiral liquid crystal is presented.

1-Alkoxy-2,5-diphenylphospholane and -phospholanium salts in rhodium-catalyzed asymmetric hydrogenation

A series of chiral enantiopure phosphinites was synthesized in four steps starting from phosphinic acid. New species were obtained as alkoxyphosphonium compounds. They can be used in the asymmetric hydrogenation of functionalized alkenes. Wiley-VCH Verlag

Solution-phase-peptide synthesis without purification of column chromatography and recrystallization by protecting amino acid esters with phosphinyl chloride

Biphenyl phosphinyl chloride (Bpp-Cl) has been successfully applied for the amino acid GAP (Group-Assisted Purification) protection. The resulting N-protected amino acid esters have been readily converted into the corresponding amino acids and peptides th

Enantiopure 1-r-H-2-c,5-t-diphenylphospholane as ligand in Rh-catalyzed asymmetric hydrogenation

Chiral enantiopure secondary phospholane 1-r-H-2-c,5-t-diphenylphospholane and the corresponding oxide are unusual and efficient ligands in the rhodium catalyzed hydrogenation of olefins.

Enantioselective Synthesis of Atropisomeric Biaryls using Biaryl 2,5-Diphenylphospholanes as Ligands for Palladium-Catalysed Suzuki-Miyaura Reactions

Here we describe the development of biaryl 2,5-diphenylphospholanes as a new class of C2-symmetric, monodentate ligands for asymmetric Suzuki-Miyaura (ASM) reactions. Screening of a series of exemplary phospholanes led to the identification of two ligands that were used to prepare a range of atropisomeric biaryl and heterobiaryl products with good to excellent levels of enantioselectivity (up to 97:3 e.r.) under mild conditions. DFT studies suggest that the formation of a constraining ligand pocket and coordination of one of the biaryl methoxy groups in the optimised ligands to the metal centre is crucial for restricting conformational freedom in the bond-forming step. (Figure presented.).

N-Phosphinyl Imine Chemistry (I): Design and Synthesis of Novel N-Phosphinyl Imines and their Application to Asymmetric aza-Henry Reaction

Novel chiral N-phosphinamide and N-phosphinyl imines have been designed, synthesized and applied to asymmetric aza-Henry reaction to give excellent chemical yields (92%- quant.) and diastereoselectivity (91% to >99%de). The reaction showed a great substra

Bis-(2,5-diphenylphospholanes) with sp2 carbon linkers: Synthesis and application in asymmetric hydrogenation

(Chemical Equation Presented) Four chiral diphosphine ligands consisting of bis(2,5-diphenylphospholan-1-yl) groups connected by the sp2 carbon linkers 2,3-quinoxaline ((S,S)-Ph-Quinox), 2,3-pyrazine ((S,S)-Ph-Pyrazine), maleic anhydride ((S,S)-Ph-MalPhos), and 1,1′-ferrocene ((S,S)-Ph-5-Fc) were synthesized, and their cationic [rhodium-(I)(COD)] complexes were prepared. These complexes were tested in asymmetric hydrogenation of functionalized olefins. [((S,S)-Ph-Quinox)Rh(COD)]BF4 showed high activity and selectivity against itaconate and dehydroamino acid substrates. The corresponding (S,S)-Ph-Pyrazine and (S,S)-Ph-MalPhOS complexes exhibited lower activities and selectivities. [((S,S)-Ph-S-Fc)Rh(COD)]BF4 showed high activity with low selectivity for these substrates, but high activity and selectivity against 2-C-substituted cinnamate salts, whereas rhodium complexes of (S,S)-Ph-Quinox and (R,R)-Ph-BPE showed low activity and selectivity against 2-C-substituted cinnamate salts.

Synthesis of enantiopure 1-r-alkyl-2-c,5-t-diphenylphospholanes and phospholanium salts through direct alkylation of phospholane

Chiral enantiopure 1-alkyl-2,5-diphenylphospholanium salts were obtained in one step through alkylation of phospholane with alkyl triflates. The resulting air-stable phosphonium salts are electron-rich trialkylphosphane precursor ligands for transition metals, and they offer a convenient route toward chiral quaternary phosphonium salts as phase-transfer agents. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

BISPHOSPHOLANES FOR USE AS CATALYSTS IN ASYMMETRIC REACTIONS

The invention is a set of novel bisphospholane ligands that can be complexed with transition metals. These complexes are useful as catalysts in asymmetric reactions such as asymmetric hydrogenation.

Enantioselective hydrogenation with self-assembling rhodium phosphene catalysts: Influence of ligand structure and solvent

Three sets of new and related chiral phospholane and phosphepine ligands have been prepared for Rh-catalyzed enantioselective hydrogenation. The size and substitution pattern of the cyclic monophosphanes were varied. More importantly, the ligands differ in the nature of the heterocyclic group linked to the trivalent phosphorus atom: 2-pyridone or 2-alkoxypyridine. In the corresponding Rh complexes, the pyridone units of two monodentate P ligands can assemble by hydrogen bonding and form chelates. In contrast, synthetic precursors bearing alkoxypyridine appendages are not able to aggregate via intramolecular hydrogen bonds. The nature of self-assembly is dependent on the nature of the P ligand and the solvent used for the hydrogenation (CH 2Cl2 vs. MeOH). These features affect the rate of the reaction as well as the enantioselectivity, which varied in the range of 0-99 % ee Complexation studies and DFT calculations were performed to explain these differences.