摘要:
Novel soluble polyester-supported chiral phosphines have been prepared and have been used in the preparation of rhodium and ruthenium catalysts. Such polymer-supported catalysts show high catalytic activities and enantioselectivities. In the case of Ru(BINAP) catalyst supported on soluble polyester, the resulting catalysts were found to be more active than those of the corresponding homogeneous Ru(BINAP) catalysts in the asymmetric hydrogenation of 2-arylpropenoic acids. These soluble polyester-supported catalysts can be easily separated from the reaction mixture and then be reused without loss of activity and selectivity.
摘要:
The present invention provides compounds of the formula wherein R is optionally substituted lower alkyl, cycloalkyl or aryl; R′ is alkyl or aryl; n is zero or an integer of 1 or 2; or an enantiomer thereof; or an enantiomeric mixture thereof. The compounds of formula (I) are bridged C2-symmetric biphenyldiphosphine analogs and, thus, may be employed as ligands to generate chiral transition metal catalysts which may be applied in a variety of asymmetric reactions. The compounds of the present invention are easily accessible in high diastereomeric and optical purity according to the methods disclosed herein.
摘要:
Method for the preparation of asymmetric alkynylated α-amino esters of the formula wherein R1 and R2 are independently optionally substituted alkyl cycloalkyl, aryl or heteroaryl, and Y is hydrogen or a nitrogen protecting group.
摘要:
New optically active phosphinite compounds which are useful in asymmetric catalysis have been synthesized and have been used in the preparation of rhodium catalysts. Such catalysts are particularly useful in enantioselective catalytic hydrogenation reactions.
摘要:
A method for the preparation of aryl methyl ketones converts a variety of ethyl arenas to the corresponding aryl methyl ketones using a dioxygen-containing gas as the oxidant. The catalyst used for the reaction is a metal complex bearing general formulas as disclosed.
摘要:
Novel, optically active phosphorous compounds of the formula, ##STR1## wherein R.sup.1 represents hydrogen atoms, straight or branched-chain alkyl groups having from 1 to 6 carbon atoms, R.sup.2 represents hydrogen atoms, halogen atoms, lower alkyl groups (1 to 6 carbon atoms), lower alkoxy groups (1 to 6 carbon atoms), hydroxy group, chiral hydroxyalkyl groups, and amino groups (1.degree., 2.degree., 3.degree.) vinyl groups or allyl groups and R.sup.3 represents phenyl groups, aryl groups, cyclohexyl groups, substituted and unsubstituted cycloalkyl groups, heteroaromatic rings, are described. The compounds of the formula serve as highly useful ligands in the preparation of ruthenium complexes which are effective catalysts for the asymmetric hydrogenation of 2-arylpropenoic acids leading to high valued 2-arylpropionic acids.
摘要:
This invention relates to (R)- and (S)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl-2,2'-diamine (R-1 and S-1) and (R)- and (S)-2,2'-bis(diarylphospinoamino)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl (R-2 and S-2) and (R)- and (S)-2,2'-bis(diaklphospinoamino)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl (R-3 and S-3); to a process for the preparation of R-1 and S-1 in which (R) or (S)-1,1'-binaphthyl-2,2'-diamine is partially hydrogenated in the presence of Adam's catalyst (5-20 wt/o of starting material) at 20-100.degree. C. for 20-100 hours in glacial acetic acid (solvent); to a process for the preparation of R-2, S-2, R-3 and S-3 in which R-1 or S-1 is reacted with chlorodiarylphosphine or chlorodialkylphosphine in the presence of n-butyllithium; and to the rhodium complexes containing 2 or 3 as effective catalysts for the asymmetric hydrogenation of prochiral substrates such as olefins to produce higher valued chiral products; and to the asymmetric catalytic hydrogenation of enamides under mild conditions using the Rh-(2) or Rh-(3) as catalyst with chemical yields as high as 100% and enantiomeric excess (e.e.) as high as 99%.
摘要:
This invention relates to (R)- and (S)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl-2,2'-diamine (R-1 and S-1) and (R)- and (S)-2,2'-bis(diarylphospinoamino)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl (R-2 and S-2) and (R)- and (S)-2,2'-bis(dialkylphospinoamino)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl (R-3 and S-3); to a process for the preparation of R-1 and S-1 in which (R) or (S)-1,1'-binaphthyl-2,2'-diamine is partially hydrogenated in the presence of Adam's catalyst (5-20 wt % of starting material) at 20-100.degree. C. for 20-100 hours in glacial acetic acid (solvent); to a process for the preparation of R-2, S-2, R-3 and S-3 in which R-1 or S-1 is reacted with chlorodiarylphosphine or chlorodialkylphosphine in the presence of n-butyllithium; and to the rhodium complexes containing 2 or 3 as effective catalysts for the asymmetric hydrogenation of prochiral substrates such as olefins to produce higher valued chiral products; and to the asymmetric catalytic hydrogenation of enamides under mild conditions using the Rh-(2) or Rh-(3) as catalyst with chemical yields as high as 100% and enantiomeric excess (e.e.) as high as 99%.
摘要:
The present invention provides bipyrimidinyl diphosphine compounds of the formula wherein R is optionally substituted alkyl, cycloalkyl, aryl or heteroaryl; R′ and R″ are independently optionally substituted alkyl, cycloalkyl, aryl or heteroaryl; or an enantiomer thereof; or an enantiomeric mixture thereof. The compounds of the formula (I) are chiral atropisomeric bipyrimidinyl diphosphine compounds and, thus, may be employed as ligands to generate chiral transition metal catalysts which may be applied in a variety of asymmetric reactions, e.g., in palladium catalyzed asymmetric allylic substitution reactions. The compounds of the present invention are easily accessible in high enantiomeric purity according to the methods disclosed herein.
摘要:
The invention relates to the compounds of formula: (I) which are as defined in the specification. Their use as chiral ligands in catalytic aryl transfer reactions to aromatic aldehydes is also described.