Methods for preparing isotopically modified 1,4-diene systems from non-isotopically modified 1,4-dienes involve selective oxidation of one or more bis-allylic position(s), or the preparation of isotopically modified 1,4-diene systems via trapping pi-allylic complexes with a source of deuterium or tritium. Such methods are useful for preparing isotopically modified polyunsaturated lipid including polyunsaturated fatty acids and polyunsaturated fatty acid derivatives.

Methods for preparing isotopically modified 1,4-diene systems from non-isotopically modified 1,4-dienes involve selective oxidation of one or more bis-allylic position(s), or the preparation of isotopically modified 1,4-diene systems via trapping pi-allylic complexes with a source of deuterium or tritium. Such methods are useful for preparing isotopically modified polyunsaturated lipid including polyunsaturated fatty acids and polyunsaturated fatty acid derivatives.

Enantiopure terphenyl presenting two ortho-located chiral axes having the following structural formula (I): their process of synthesis and their use as mono or bidentate ligands for asymmetric organometallic reactions, as organocatalysts, as chiral base and as generator, with metal, of isolable chiral metallic complexes for applications in asymmetric catalysis and others.

The present invention generally relates to processes for the recovery of rhodium from a catalyst purge stream from a C6 or higher olefin hydroformylation process. In one embodiment, the process comprises (a) treating a catalyst-containing liquid purge stream from the hydroformylation process, wherein the catalyst comprises a precious metal and an organophosphorous ligand, with an oxidant in the presence of a separate liquid aqueous phase comprising a halide-free acid at a sufficient temperature to effect oxidation of a majority of the contained organophosphorous ligand, wherein the halide-free acid is a C1-C6 organic acid or phosphorous acid; (b) recovering the aqueous phase; (c) contacting the aqueous phase with a separate organic phase by mixing the two phases under a syngas atmosphere, wherein the separate organic phase comprises water-insoluble, hydrolysable organophosphorous ligand and recycled olefin from a hydroformylation process; and (d) separating the organic phase to be recycled back to a hydroformylation process.

The present invention refers to the use of an epoxide in order to reduce the formation of heavy ends in a continuous hydroformylation process, where an olefin or olefin mixture is reacted with carbon monoxide and hydrogen in the presence of a rhodium complex catalyst, comprising at least one organobisphosphite ligand, in order to produce an aldehyde. Said epoxide is added to the reaction mixture in an amount of 0.01-1.5 wt %, reducing the formation of heavy ends by 10-80%.

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##

A hydroformylation process can be used for short-chain olefins, especially C2 to C5 olefins, wherein the catalyst system is heterogenized on a support that contains a porous ceramic material. Systems can also be used for carrying out said process.

The present invention refers to a method for reducing heavy end formation and catalyst loss in a continuous hydroformylation process, where an olefin or an olefin mixture is reacted with carbon monoxide and hydrogen in a reactor assembly (1) in the presence of a rhodium complex catalyst, comprising at least one organobisphosphite ligand, in order to produce an aldehyde. Said method comprising the addition of an epoxide to the reaction mixture and the continuous or discontinuous removal of early heavy ends.

[Problem] To provide a complex compound useful as a catalyst for a hydrophosphorylation reaction and a process for producing the same.

[Means to Solve the Problem] A complex compound of the present invention is a complex compound of a resin fine particle represented by the following general formula (1):

##STR00001## wherein, R.sup.1 represents a substituted or unsubstituted hydrocarbon group, R.sup.2 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, R.sup.3 and R.sup.4 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and based on the total of 100% of the values of n and m, the value of n is within the range of 20 to 100%, the value of m is within the range of 0 to 80%, and * represents bonding with the surface of the resin fine particle and a transition metal.

Disclosed are a spiro-bisphosphorous compound, and a preparation and application thereof. The spiro-bisphosphorous compound is expressed in formula (I), (II) or (III).

##STR00001##