Chiral diphenyldiphosphines and d-8 metal complexes thereof

Details Chiral diphenyldiphosphines and d-8 metal complexes thereof Chiral diphenyldiphosphines and d-8 metal complexes thereof

2001-07-06

2003-02-04

Vollano, Jean F. (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Phosphorus containing

C549S218000, C556S404000, C568S017000

Reexamination Certificate

active

06515183

ABSTRACT:

The present invention relates to mono- and di-(halogenmethyl)-diphenyldiiodides, -dibromides and -diamines; mono- and di-(hydroxymethyl)-diphenyldiiodides, -dibromides and -diamines and mono- and di-(aminomethyl)-diphenyldiiodides, -dibromides and -diamines; mono- and di-(hydroxymethyl)-diphenyldiphosphines and mono- and di-(aminomethyl)-diphenyldiphosphines, as well as 2-hydroxypropane-1,3-dioxyl-diphenyldiphosphines; mono- and di-(hydroxymethyl)-diphenyldiphosphines and mono- and di-(aminomethyl)-di-phenyldiphosphines, as well as 2-hydroxypropane-1,3-dioxyl-diphenyldiphosphines, the hydroxyl groups or amino groups of which are provided with functional groups via a bridging group; inorganic and organic polymeric carriers which are immobilised with said diphosphines; metal complexes of the monomeric and immobilised diphosphines; and the use of the metal complexes as homogeneous and enantioselective catalysts in the synthesis of organic compounds, for example hydrogenation.
In Pure and Appl. Chem., Vol. 68, No. 1, pp. 131-138 (1996), R. Schmid et al. describe atropisomeric 6,6′-dimethyl- and 6,6′-dimethoxy-2,2′-diphenyldiphosphines as chiral ligands in metal complexes, which are used for the hydrogenation of prochiral ketones and olefins, whereby high optical yields may be attained. The catalysts can only be extracted from the reaction mixtures with difficulty and incompletely, so that it is impossible to reuse them for further reactions.
In WO 98/01457, B. Pugin et al. describe the functionalisation of chiral ferrocenyl-diphosphines as ligands for metal complexes and the immobilisation on inorganic and organic carriers, which may be used as enantioselective hydrogenation catalysts. These catalysts may be easily separated from the reaction mixture and reused.
It has now been found that, in a simple manner, functionalised 2,2′-diphenyldiphosphines can be prepared and may be immobilised both on inorganic and on organic polymeric carriers, and can also be used as water-soluble and/or extractable and/or adsorbable ligands/catalysts. The immobilised diphosphine ligands bond with d-8 metals such as rhodium, ruthenium and iridium complexes which may be used as highly effective catalysts in enantioselective hydrogenation of carbon-carbon, carbon-nitrogen or carbon-oxygen double bonds. The selectivity, activity and total yield for immobilised systems are surprisingly high.
The catalysts may be easily separated from the reaction solution and reused. Almost no metal or ligand losses occur. In addition, immobilised diphenyldiphosphine ligands especially on inorganic carriers have surprisingly high stability, which is especially important for reusage. Therefore, using these immobilised catalysts, large-scale hydrogenation may be carried out especially economically.
The reaction to be catalysed may be carried out even heterogeneously or homogeneously through the choice of polymer, for example in the case of polymer-bound diphosphine ligands. The polymer may be prepared in such a way, or also subsequently specifically modified in such a way that the polymer-bound catalyst dissolves in the reaction medium, and can be easily separated after the reaction by filtration, ultrafiltration, extraction or adsorption on carriers, and then reused. The catalysts can be reused several times. Through the choice of polymer, the catalyst may be optimally adapted to the reaction medium during the hydrogenation step, and then completely separated, which is important in particular for hydrogenation carried out on a large scale.
The production of these immobilised or extractable and/or adsorbable diphenyldiphosphines is made possible only by providing correspondingly functionalised diphenyldiphosphines. Therefore, particular importance is placed on these intermediates and their preparation.
In all cases, recovery of the noble metals contained therein is simplified if the catalyst has to be exchanged after frequent recycling. Frequently, further purification of the hydrogenated product can be dispensed with, since the catalyst can be removed practically quantitatively.
A first object of the invention is compounds of formula 1,
wherein
R
1
is methyl chloride, methyl bromide or methyl iodide, R
2
is C
1
-C
4
-alkyl or C
1
-C
4
-alkoxy or has the same significance as R
1
, and R
3
is Br, I or —NH
2
.
R
1
is preferably methyl bromide. R
2
is preferably alkyl, and as alkyl preferably signifies ethyl and most preferably methyl. R
2
as alkoxy preferably signifies methoxy or ethoxy. R
3
is preferably Br or I.
The preparation thereof may be effected in known manner by the radical halogenation of the methyl groups of 2,2′-di-R
3
-6,6′-dimethyl-diphenyl with appropriate halogenation agents, for example Cl
2
, Br
2
, I
2
, interhalogen compounds such as ClBr, ClI, or SOCl
2
, SOBr
2
, SOI
2
, and organic halogen compounds such as CF
3
CL, CF
3
Br, CF
3
I, CCl
3
I, as well as N-halogenated acid amides, for example N-chloro-, -bromo- and -iodosuccinimide. Depending on the amount of halogenation agent, mono- or dihalogen-methyl-diphenyls are primarily obtained, whereby mixtures of the compounds may be separated by distillation, by chromatographic methods or by crystallisation. The oily or crystalline compounds of formula I are valuable initial products for the production of atropisomeric diphosphines.
A further object of the invention is compounds of formula II,
wherein
R
3
is Br, I or —NH
2
, R
4
is hydroxymethyl, aminomethyl, hydroxy-, amino- or cyano-C
2
-C
8
-alkoxy, hydroxy-, amino- or cyano-C
2
-C
8
-alkoxymethyl, or hydroxy-, amino- or cyano-C
2
-C
8
-alkylaminomethyl, and R
5
has the same significance as R
4
, or R
5
is C
1
-C
4
-alkyl or C
1
-C
4
-alkoxy, or R
4
and R
5
together are HOCH(CH
2
—O—)
2
, H
2
NCH(CH
2
—O—)
2
, or hydroxy-, amino- or cyano-C
2
-C
8
-alkylOCH(CH
2
—O—)
2
.
R
3
is preferably Br or I and especially I. C
2
-C
8
-alkyl in the hydroxy-, amino- or cyanoalkyl groups is preferably C
2
-C
6
-alkyl, more preferably C
2
-C
4
-alkyl, for example C
2
-, C
3
-alkyl or C
4
-alkyl. R
5
as C
1
-C
4
-alkyl or C
1
-C
4
-alkoxy may be for example methyl, ethyl, propyl, butyl, methoxy, ethoxy, propyloxy and butyloxy; methyl and methoxy are preferred. If R
5
signifies alkyl, R
4
is preferably hydroxymethyl, aminomethyl, hydroxy-, amino- or cyano-C
2
-C
8
-alkoxymethyl, or hydroxy-, amino- or cyano-C
2
-C
8
-alkylaminomethyl If R
5
signifies alkoxy, R
4
is preferably amino- or cyano-C
2
-C
8
-alkoxy. The hydroxy, amino or cyano groups are preferably primary groups.
The compounds of formula II may be produced by known synthesis methods. Thus, the methyl halide group in the compounds of formula I can be hydroxylated or aminated in known manner. These hydroxy or amino compounds, or the known 2-alkoxy-2′-hydroxy-6,6′-substituted diphenyl, or the known 2,2′-dihydroxy-6,6′-substituted diphenyl, or a compound of formula
which is obtainable by reacting 2,2′-dihydroxy-6,6′-substituted diphenyl with epichlorohydrin or 1,3-dichloro-2-hydroxypropane, is reacted with cyanoalkenyl and then the cyano group is hydrogenated, or reacted with hydroxyhalogen- or aminohalogen-alkanes, or with ethylene oxide or aziridine. The HO group may be substituted by a NH
2
group in known manner, for example first of all halogenated and then reacted with 1,1′-carbonyl-diimidazole; hydrolysis then yields the free amine.
The compounds of formula II are eminently suitable for producing corresponding diphenyldiphosphines, in which the functional groups may undergo prior or subsequent modification in conventional manner by conversion into other functional groups or by a reaction with difunctional chain extenders, for example epoxides, hydroxyalkyl cyanates, halo-alkanols, halo-alkane nitrites, halo-alkane phthalimides, dicarboxylic acids or diisocyanates. The phosphine groups are introduced in known manner [see Pure and Appl. Chem., Vol. 68, No. 1, pp. 131-138 (1996)] by reacting compounds of formula II with lithium alkyls, for example lithi

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