New Monodentate P,C‐Stereogenic Bicyclic Phosphanes: 1‐Phenyl‐1,3a,4,5,6,6a‐hexahydrocyclopenta[b]phosphole and 1‐Phenyloctahydrocyclopenta[b]phosphole

Abstract

Racemic 1-phenyl-1,3a,4,5,6,6a-hexahydrocyclopenta[b]-phosphole (4) was separated into enantiomerically pure 1-phenyl-1,3a,4,5,6,6a-hexahydrocyclopenta[b]phosphole 1-oxides [(R P )-6 and (S P )-6] by an oxidative resolution procedure involving treatment of 4 with menthyl bromoacetate, crystallization of the resulting diastereoisomeric phosphonium bromides 8, and stereoselective hydrolysis of the diastereomerically pure salts to the corresponding enantiomerically pure phosphane oxides. Stereoretentive reduction of P=O in

Enantioselective Phosphine Organocatalysis

“…27 As far as we know, these are the only two reports published so far on this very challenging enantioselective carbon-carbon bond forming reaction.…”

Synthesis of Chiral Heterocyclic Phosphines for Application in Asymmetric Catalysis

“…An alternative for the synthesis of fused cyclopentyl phosphetanes via their corresponding phospholene derivatives was discovered by Pietrusiewicz et al via a cyclopentaannelation route starting either from phospholane oxide 1a or phospholane sulfide 1b (Scheme 3.14) [64]. The more hindered dimethylsubstituted BPOs 6a and 7a were prepared according to the pathway shown in Scheme 3.15 [65].…”

A study on the optical resolution of 1-isopropyl-3-methyl-3-phospholene 1-oxide and its use in the synthesis of borane and platinum complexes

“…As a new compound, the isopropyl-phospholene oxide (3) was characterized by 1 H, 13 C and 31 P NMR spectroscopy, as well as HRMS.…”

“…Many examples can be found in the literature for the resolution of 3 cyclic P-chiral phosphines, phosphine oxides and phosphonium salts via the formation of covalent diasteromers [11][12][13], diastereomeric coordination [14][15][16][17][18][19], molecular complexes [10,20,21] or diastereomeric salts [22][23][24][25][26][27].…”

“…In the literature, the synthesis of a few optically active P-chiral heterocyclic ligands was described and the transition metal complexes of these P(III)-compounds were used as catalysts mainly in enantioselective hydrogenation reactions [11,13,16,18,21,[28][29][30][31][32]. There are only a few examples for P-heterocyclic ligands that were used in hydroformylation [5].…”