The invention is directed to methods of converting a carboxylic acid group in a compound, via a redox active ester, to a corresponding boronic ester by treatment with bis(pinacolato)diboron-alkyllithium complex in the presence of a ligand, a Ni(II) salt or a copper salt, and an Mg(II) salt, in the presence of an alkyllithium or a lithium hydroxide or alkoxide salt. The product pinacolato boronate ester can be cleaved to provide a boronic acid. The invention is also directed to methods of preparing various compounds of medical value comprising boronic acid groups, and to novel boronic-acid containing compounds of medicinal value, including an atorvastatin boronic acid analog, a vancomycin aglycone boronic acid analog, and boronic acid containing elastase inhibitors mCBK319, mCBK320, mCBK323, and RPX-7009.

Disclosed is a method for preparing a borate ester on the basis of a tricyclopentadienyl rare earth metal complex, the method comprising the following steps: uniformly stirring and mixing a catalyst, a borane and a carbonyl compound for reaction to prepare a borate ester, wherein the catalyst is a tricyclopentadienyl rare earth metal complex; and the molecular formula of the tricyclopentadienyl rare earth metal complex can be expressed as: Ln(Cp).sub.3, wherein Ln represents a rare metal selected from one of lanthanide elements. The preparation method has a higher catalytic activity, mild reaction conditions, a product that is easy to post-treat, a short reaction time, a low catalyst consumption amount, and a good range of applicable substrates, and can be used for industrial production.

Provided are a 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-based monophosphine ligand and intermediates thereof, and preparation methods and uses of the same. The monophosphine ligand is a compound represented by formula I or formula I′, or an enantiomer, a raceme or a diastereoisomer thereof, including phosphonite ligands, phosphite ligands, phosphoramidite ester ligands, phosphoric acid and phosphonic amide. The monophosphine ligand is prepared with a known 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-7,7′-diol derivative as a raw material through a scheme in which the compound presented by formula II acts as an intermediate. The present disclosure provides a novel monophosphine ligand, which can be used as a ligand in a metal-catalysed organic reactions or in directly catalyzing an organic reaction, especially as a chiral monophosphine ligand widely used in many chiral catalytic reactions such as asymmetric addition, asymmetric hydrogenation, asymmetric coupling, and asymmetric allyl alkylation, having economic practicality and industrial application prospects. ##STR00001##

Disclosed is a method for preparing a borate ester on the basis of a tricyclopentadienyl rare earth metal complex, the method comprising the following steps: uniformly stirring and mixing a catalyst, a borane and a carbonyl compound for reaction to prepare a borate ester, wherein the catalyst is a tricyclopentadienyl rare earth metal complex; and the molecular formula of the tricyclopentadienyl rare earth metal complex can be expressed as: Ln(Cp).sub.3, wherein Ln represents a rare metal selected from one of lanthanide elements. The preparation method has a higher catalytic activity, mild reaction conditions, a product that is easy to post-treat, a short reaction time, a low catalyst consumption amount, and a good range of applicable substrates, and can be used for industrial production.

Metal-organic framework (MOFs) compositions based on postsynthetic metalation of secondary building unit (SBU) terminal or bridging OH or OH.sub.2 groups with metal precursors or other post-synthetic manipulations are described. The MOFs provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of asymmetric organic transformations, including the regioselective boryiation and siiylation of benzyiic CH bonds, the hydrogenation of aikenes, imines, carbonyls, nitroarenes, and heterocycles, hydroboration, hydrophosphination, and cyclization reactions. The solid catalysts can also be integrated into a flow reactor or a supercritical fluid reactor.

Provided are a 3,3,3,3-tetramethyl-1,1-spirobiindane-based monophosphine ligand and intermediates thereof, and preparation methods and uses of the same. The monophosphine ligand is a compound represented by formula I or formula I, or an enantiomer, a raceme or a diastereoisomer thereof, including phosphonite ligands, phosphite ligands, phosphoramidite ester ligands, phosphoric acid and phosphonic amide. The monophosphine ligand is prepared with a known 3,3,3,3-tetramethyl-1,1-spirobiindane-7,7-diol derivative as a raw material through a scheme in which the compound presented by formula II acts as an intermediate. The present disclosure provides a novel monophosphine ligand, which can be used as a ligand in a metal-catalysed organic reactions or in directly catalyzing an organic reaction, especially as a chiral monophosphine ligand widely used in many chiral catalytic reactions such as asymmetric addition, asymmetric hydrogenation, asymmetric coupling, and asymmetric allyl alkylation, having economic practicality and industrial application prospects.

##STR00001##

The invention is directed to methods of converting a carboxylic acid group in a compound, via a redox active ester, to a corresponding boronic ester by treatment with bis(pinacolato)diboron-alkyllithium complex in the presence of a ligand, a Ni(11) salt or a copper salt, and an Mg(11) salt, in the presence of an alkyllithium or a lithium hydroxide or alkoxide salt. The product pinacolato boronate ester can be cleaved to provide a boronic acid. The invention is also directed to methods of preparing various compounds of medical value comprising boronic acid groups, and to novel boronic-acid containing compounds of medicinal value, including an atorvastatin boronic acid analog, a vancomycin aglycone boronic acid analog, and boronic acid containing elastase inhibitors mCBK319, mCBK320, mCBK323, and RPX-7009.

Metal-organic framework (MOFs) compositions based on postsynthetic metalation of secondary building unit (SBU) terminal or bridging OH or OH.sub.2 groups with metal precursors or other post-synthetic manipulations are described. The MOFs provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of asymmetric organic transformations, including the regioselective boryiation and siiylation of benzyiic CH bonds, the hydrogenation of aikenes, imines, carbonyls, nitroarenes, and heterocycles, hydroboration, hydrophosphination, and cyclization reactions. The solid catalysts can also be integrated into a flow reactor or a supercritical fluid reactor.

A 1,2-regioselective organolanthanide-catalyzed azine dearomatization process using pinacolborane is disclosed.

The invention is directed to methods of converting a carboxylic acid group in a compound, via a redox active ester, to a corresponding boronic ester by treatment with bis(pinacolato)diboron-alkyllithium complex in the presence of a ligand, a Ni(II) salt or a copper salt, and an Mg(II) salt, in the presence of an alkyllithium or a lithium hydroxide or alkoxide salt. The product pinacolato boronate ester can be cleaved to provide a boronic acid. The invention is also directed to methods of preparing various compounds of medical value comprising boronic acid groups, and to novel boronic-acid containing compounds of medicinal value, including an atorvastatin boronic acid analog, a vancomycin aglycone boronic acid analog, and boronic acid containing elastase inhibitors mCBK319, mCBK320, mCBK323, and RPX-7009.