Taming functionality: easy-to-handle chiral phosphiranes

Abstract

Enantiopure chiral phosphiranes possessing a binaphthyl backbone demonstrate remarkable thermal stability, are highly resistant to air-oxidation and are effective ligands in catalytic asymmetric hydrosilylations.

MOP-phosphonites: A novel ligand class for asymmetric catalysis

“…The ligands coordinate via the phosphorus donor atom in an expected monodentate manner to form a pseudo-square-planar configuration around the palladium. Pd-P bond lengths are similar in all complexes (2.2354(7) to 2.2542 (8) Å) and are found to be shorter than for the two MOP-phosphine allylpalladium complexes previously reported (2.3098 (9) and 2.328(1) Å); 13 however, shortened Pd-P bond lengths are anticipated for phosphonite complexes due to their stronger π-acceptor character. 14 Pd-C bond lengths show the dominant trans effect of the P-ligand relative to the chloride; the bonds trans to the phosphorus are about 0.1 Å longer compared to the bonds in the cis position.…”

Inversion of Configuration at the Phosphorus Nucleophile in the Diastereoselective and Enantioselective Synthesis of P‐Stereogenic syn‐Phosphiranes from Chiral Epoxides

“…[21] Chiral phosphiranes are especially unusual, [22] so our convenient one-pot synthesis is potentially useful [23] for expanding their currently limited applications in asymmetric catalysis. [24,25] We are now investigating this possibility,aswell as the intriguing role of Li + and other Lewis acids in mediating phosphirane formation.…”

“…[18] Although phosphiranes have unique stereoelectronic properties,with smaller cone angles and higher Pinversion barriers than their acyclic analogues,a nd are thought to be poorer s-donors and better p-acceptors, [19] their use as ligands [20] in metal-catalyzed reactions is rare. [24,25] We are now investigating this possibility,aswell as the intriguing role of Li + and other Lewis acids in mediating phosphirane formation. [24,25] We are now investigating this possibility,aswell as the intriguing role of Li + and other Lewis acids in mediating phosphirane formation.…”

Zirconium-Catalyzed Alkene Hydrophosphination and Dehydrocoupling with an Air-Stable, Fluorescent Primary Phosphine

“…Primary phosphines can be difficult to handle due to toxicity and facile oxidation that renders many simple derivatives pyrophoric. A vigorous effort to understand and expend the family of airstable primary phosphines emerged in recent years to avail greater use of these molecules [12][13][14][15]. Among this class of primary phosphines are 8-[(4-phosphino)phenyl]-4,4-dimethyl-1,3,5,7-tetramethyl-2,6-diethyl-4-bora-3a,4a-diaza-s-indacene (2) [12,[15][16][17][18] and (2′-methoxy-[1,1′-binaphthalen]-2-yl)phosphine (3) [19,20] (Figure 1).…”

“…As expected both products retain their fluorescence. Products 4 and 5 were excited at 485 nm and displayed a maximum emission at 529 and 534 nm, respectively, similar to their precursor 2 ( Figures S3 and S6) [14].…”