502159-06-0

Upstream product

• 22348-32-9 (S)-diphenylprolinol 
• 100-58-3 phenylmagnesium bromide 
• 137496-68-5 2-[hydroxy(diphenyl)methyl]pyrrolidine-1-carboxylic acid tert-butyl ester 

Downstream Products

• 1213238-45-9 C₄₀H₃₇IN₂O₄P₂ 
• 866219-15-0 C₄₃H₄₈N₃O₆PSi 

Relevant academic research and scientific papers

COMPOUNDS, COMPOSITIONS AND METHODS FOR SYNTHESIS

The present disclosure, among other things, provides technologies for synthesis, including reagents and methods for stereoselective synthesis. In some embodiments, the present disclosure provides compounds useful as chiral auxiliaries. In some embodiments, the present disclosure provides reagents and methods for oligonucleotide synthesis. In some embodiments, the present disclosure provides reagents and methods for chirally controlled preparation of oligonucleotides. In some embodiments, technologies of the present disclosure are particularly useful for constructing challenging internucleotidic linkages, providing high yields and stereoselectivity.

Chiral amino alcohol derived bis-phosphoramidite pincer palladium complexes and their applications in asymmetric allylation of aldimines

Novel P-stereogenic bis-phosphoramidite pincer palladium complexes 1 and 2 derived from (S)-(-)-α,α-diphenyl-2-pyrrolidinemethanol and (S)-(+)-indolinemethanol, respectively, were synthesized in reasonable yields (i.e., 55-62%) by using a flexible, modular synthetic approach and were characterized by X-ray crystal structure determination. Reacting (S)-(+)-indolinemethanol with PCl3 leads to the formation of a novel P-chiral building block, which exhibits good thermal stability of its stereochemical features. This enabled the design and development of new P-chiral bisphosphoramidite pincer arene ligands and their corresponding metal complexes. The molecular structure of the new indolinemethanol-derived phosphoramidite pincer metal complex screens quadrants I and III, which is in contrast to the previously reported L-proline-derived P-chiral ligands that screen quadrants II and IV. The bis-phosphoramidite pincer palladium, complexes 1 and 2 are active catalysts for asymmetric homoallylation of sulfonimines, where low (ee 33%) or no enantioselectivity was observed for reactions catalyzed by 2 and 1, respectively. Preliminary catalytic results revealed that enantiomeric excess values varied by using differently functionalized sulfonimines, suggesting that, both electronic properties and steric congestion of sulfonimines affect, the transition state of the electrophilic attack of the 1nallyl Pd intermediate in the allylation.

Diphenylprolinol-derived symmetrical and unsymmetrical chiral pincer palladium(II) and nickel(II) complexes: Synthesis via one-pot phosphorylation/metalation reaction and C-H activation

The symmetrical P-stereogenic bis-phosphoramidite PCP pincer Pd(II) complexes 1 and 2 were easily prepared by a four-component, one-pot phosphorylation/palladation' procedure via C-H bond activation of the related ligands. In this synthetic procedure, (S)-diphenyl(pyrrolidin-2-yl)methanol was first phosphonated with PCl3 to afford the expected phosphorochloridate adduct, which then reacted in situ with resorcinol or disubstituted resorcinol, followed by treatment with PdCl2. The first examples of the unsymmetrical P-stereogenic phosphoramidite- and imidazoline-containing PCN pincer Pd(II) complex 3 and Ni(II) complex 4 could be obtained in a similar manner by using a chiral imidazoline-containing m-phenol derivative instead of resorcinol as a backbone. 31P NMR of the complexes confirmed the formation of a single diastereoisomer concerning the P-stereogenic center, and its absolute configuration was determined by an X-ray crystal structure determination. Preliminary investigations on the use of these complexes in the asymmetric allylation indicated that the unsymmetrical pincer Pd complex 3 exhibited higher catalytic activity than the related symmetrical ones. On the other hand, the more bulky Pd complex 2 gave better enantioselectivity, especially in the allylation of 4-nitrobenzenesulfonimine (69% ee).

Stereocontrolled solid-phase synthesis of oligonucleoside H-phosphonates by an oxazaphospholidine approach

(Chemical Equation Presented) Stereodefined oligonucleoside H-phosphonates were synthesized on a solid support using diastereopure nucleoside 3′-O-oxazaphospholidine monomers. Several stereodefined backbone-modified analogues were obtained with the oligonucleoside H-phosphonates as precursors (see scheme; BPRO = protected nucleobase, DMTr = 4,4′- dimethoxytrityl, Th = thymin-1-yl, TfO- = triflate).

Chiral diphosphites and diphosphoramidites as cheap and efficient ligands in Rh-catalyzed asymmetric olefin hydrogenation

Chiral diphosphites and diphosphoramidites derived from BINOL or diphenylprolinol are efficient ligands in asymmetric Rh-catalyzed olefin hydrogenation, provided the proper achiral backbone is chosen. The Royal Society of Chemistry 2006.

New modular P-chiral ligands for Rh-catalyzed asymmetric hydrogenation

New modular P-chiral ligands have been prepared from commercially available (S)-α,α-diphenylprolinol. With these new types of ligands, up to 95% ee was achieved in the Rh-catalyzed asymmetric hydrogenation of functionalized olefins.

A modular approach to structurally diverse bidentate chelate ligands for transition metal catalysis

A modular approach to a new class of structurally diverse bidentate P/N, P/P, P/S, and P/Se chelate ligands has been developed. Starting from hydroquinone, various ligands were synthesized in a divergent manner via orthogonally bis-protected bromohydroqui