Natural compounds in the synthesis of chiral organophosphorous ligands

Abstract

Methods for the synthesis of chiral organophosphorus Methods for the synthesis of chiral organophosphorus compounds based on natural optically active compounds compounds based on natural optically active compounds (hydroxy acids, amino acids and their derivatives, mono-and (hydroxy acids, amino acids and their derivatives, mono-and disaccharides, mono-and diterpenoids, steroids) are discussed. disaccharides, mono-and diterpenoids, steroids) are discussed. Particular attention is given to the synthesis of bisphosphines and Particular attention is given to the synthesis of bisphosphines and bisphosphinites. These compounds serve as ligands for transition bisphosphinites. These compounds serve as ligands for transition metal complexes, which catalyse asymmetric hydrogenation. Data metal complexes, which catalyse asymmetric hydrogenation. Data on the enantioselectivity of hydrogenation of unsaturated precur-on the enantioselectivity of hydrogenation of unsaturated precursors of amino acids and unsaturated prochiral acids as well as on sors of amino acids and unsaturated prochiral acids as well as on the enantioselectivity of hydrosilylation of ketones are surveyed. the enantioselectivity of hydrosilylation of ketones are surveyed. The bibliography includes 77 references The bibliography includes 77 references. .

Isosteviol acylphosphonates

“…The mixture was refluxed for 2 h. The excess of PCl 3 was removed in vacuo. The thickened organic layer was separated and treated with hexane to give compound 2 (0.09 g, 87%) with a small impurity of iso steviol (1).…”

“…The attractive properties of this compound include 100% enantiomeric purity, a sufficiently high content in, and easy extraction from, the natural raw material, the presence of func tionalizable reactive groups, the conformational rigidity of the carbon skeleton, and the configurational stability of the chiral centers. 3-5 Earlier, 6 we have described the first example of the phosphorylation of isosteviol (1).…”

“…Recently, we have investigated the reactivity of the diterpenoid isosteviol (1), which can be easily prepared from an accessible natural raw material (the plant Stevia rebaudiana Bertoni 2 ). The attractive properties of this compound include 100% enantiomeric purity, a sufficiently high content in, and easy extraction from, the natural raw material, the presence of func tionalizable reactive groups, the conformational rigidity of the carbon skeleton, and the configurational stability of the chiral centers.…”

Unusual reaction of 8-chloro-2-cyclohexyl-4-phenylbenzo[e]-1,2-oxaphosphinine-2-oxide with tetramethylenebis(magnesium bromide)

“…Achiral (R 3 P=O), prochiral (R 2 R 1 P=O) and chiral (R 1 R 2 R 3 P=O) phosphine oxides are the main precursors in the syntheses of corresponding phosphines, [1][2][3][4][5][6][7][8][9][10][11] which are widely used as ligands in metal complex catalysts 2,4,6,10,12 and neutral extracting agents for rare-earth metals. [13][14][15][16][17] Phosphine oxides can also be used as ligands in reactions catalysed by palladium and molybdenum complexes.…”

Application of Hydroxyporphyrins-based Phosphite-type Ligands to Asymmetric Pd-Catalyzed Allylic Substitution Reactions

“…Therefore, the development of novel phosphorus-containing stereoselectors is ongoing and still in high demand. [11,[14][15][16][17][18] Chiral phosphite-type compounds constitute a class of prominent ligands because they are favorably distinguished by resistance to oxidation, pronounced π-acidity, and are inexpensive. Also, they can be easily prepared from readily available starting materials via simple condensation processes, including those involving parallel and solidphase synthetic procedures.…”