This invention provides enantioenriched Mannich adducts with quaternary stereogenic centers and novel methods of preparing the compounds. Methods include the method for the preparation of a compound of formula (I):

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comprising treating a compound of formula (II):

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with a transition metal catalyst under alkylation conditions.

A method for producing a compound (4), which comprises allowing a compound (1) to react with hydrogen gas in an inert solvent, in the presence of a specific chiral ligand and a ruthenium catalyst, or in the presence of an asymmetric transition metal complex catalyst previously generated from the chiral ligand and the ruthenium catalyst. ##STR00001##

Provided is a method for producing an optically active substance, the method including an asymmetric induction, wherein an asymmetry inducer is allowed to act on a chiral molecule having a half-life of enantiomeric excess of shorter than 10 hours, thereby increasing abundance of one enantiomer of the chiral molecule. According to this method, one enantiomer of a chiral molecule that is susceptible to racemization can be selectively and efficiently obtained.

The present disclosure relates to a novel, highly efficient and enantiospecific borylation method to synthesize a wide range of enantiopure alfa-amino tertiary boronic esters, and novel alfa-amino tertiary boronic acids and esters prepared by the method. More specifically, highly enantiospecific borylation of configurationally stable -N-Boc substituted tertiary organolithium species and HBpin has been developed to synthesize various alfa-amino tertiary boronic esters through the formation of a new CB bond with excellent enantiopurities.

The present disclosure relates to a novel, highly efficient and enantiospecific borylation method to synthesize a wide range of enantiopure alfa-amino tertiary boronic esters, and novel alfa-amino tertiary boronic acids and esters prepared by the method. More specifically, highly enantiospecific borylation of configurationally stable -N-Boc substituted tertiary organolithium species and HBpin has been developed to synthesize various alfa-amino tertiary boronic esters through the formation of a new CB bond with excellent enantiopurities.

A compound represented by a formula [1D] as shown below (wherein R.sup.1A, R.sup.1B, R.sup.2A, R.sup.2B, R.sup.3A and R.sup.3B represent a hydrogen atom, an optionally substituted C.sub.1-6 alkyl group, and the like) is useful as an intermediate for producing a thionucleoside, and the production method of the present invention is useful as a method for producing a thionucleoside. ##STR00001##

A compound represented by a formula [1D] as shown below (wherein R.sup.1A, R.sup.1B, R.sup.2A, R.sup.2B, R.sup.3A and R.sup.3B represent a hydrogen atom, an optionally substituted C.sub.1-6 alkyl group, and the like) is useful as an intermediate for producing a thionucleoside, and the production method of the present invention is useful as a method for producing a thionucleoside. ##STR00001##

The invention comprises novel chiral metal complex compounds of the formula

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wherein M, PR.sup.2, R.sup.3 and R.sup.4 are outlined in the description, its stereoisomers, in the form as a neutral complex or a complex cation with a suitable counter ion. The chiral metal complex compounds can be used in asymmetric reactions, particularly in asymmetric reductions of ketones, imines or oximes.

The present invention relates to a chiral spiro phosphine-nitrogen-sulfur (PNS) tridentate ligand, preparation method and application thereof. The PNS tridentate ligand is a compound represented by Formula I or Formula II, their racemates, optical isomers, or catalytically acceptable salts thereof. The ligand has a primary structure skeleton characterized as a chiral spiro indan skeleton structure with a thio group. The chiral spiro phosphine-nitrogen-sulfur tridentate ligand can be synthesized by reacting racemic or optical active compound 7-diary/alkyl phosphine-7-amino-1, 1-spiro-dihydro-indene compound having a spiro-dihydro-indene skeleton as the starting material. The chiral spiro PNS tridentate ligand being complex with transition metal salt can be used in an asymmetric catalytic hydrogenation reaction for catalyzing carbonyl compound. In particular, in asymmetric hydrogenation reaction process, being complex with iridium for catalyzing -alkyl--keto ester can obtain a high catalytic activity (a catalyst amount of 0.0002% mol) and high enantioselectivity (up to 99.9% ee) result. So the present invention has a practical value for industrial and commercial production. ##STR00001##

The present invention relates to a chiral spiro phosphine-nitrogen-sulfur (PNS) tridentate ligand, preparation method and application thereof. The PNS tridentate ligand is a compound represented by Formula I or Formula II, their racemates, optical isomers, or catalytically acceptable salts thereof. The ligand has a primary structure skeleton characterized as a chiral spiro indan skeleton structure with a thio group. The chiral spiro phosphine-nitrogen-sulfur tridentate ligand can be synthesized by reacting racemic or optical active compound 7-diary/alkyl phosphine-7-amino-1, 1-spiro-dihydro-indene compound having a spiro-dihydro-indene skeleton as the starting material. The chiral spiro PNS tridentate ligand being complex with transition metal salt can be used in an asymmetric catalytic hydrogenation reaction for catalyzing carbonyl compound. In particular, in asymmetric hydrogenation reaction process, being complex with iridium for catalyzing -alkyl--keto ester can obtain a high catalytic activity (a catalyst amount of 0.0002% mol) and high enantioselectivity (up to 99.9% ee) result. So the present invention has a practical value for industrial and commercial production. ##STR00001##