# US 5,710,339 A · Bisphosphines as catalysts for asymmetric reactions

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- Number: US 5,710,339 A
- Document ID: US5710339A
- Status: Granted
- Kind: A
- Application number: 08/664,073
- Filed: 1996-06-13
- Granted: 1998-01-20
- Earliest claimed: 1995-06-20
- Assignees: Bayer Aktiengesellschaft
- Inventors: Christian Laue; Georg Schroder; Dieter Arlt
- Web page: https://patentgrep.com/patent/US5710339A

## CPC

- C07F 15/0053: {without a metal-carbon linkage}
- C07B 53/00: Asymmetric syntheses
- C07C 51/36: by hydrogenation of carbon-to-carbon unsaturated bonds
- C07F 9/5027: {Polyphosphines}
- C07F 15/004: {without a metal-carbon linkage}
- C07F 15/008: {without a metal-carbon linkage}
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C07B: GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR (preparation of carboxylic acid esters by telomerisation C07C67/47; telomerisation C08F)
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

The invention relates to enantiomerically pure bisphosphines of the general formula (I) ##STR1## where R is as defined in the description, a process for their preparation and their use in metal complexes as catalysts for asymmetric reactions, in particular asymmetric hydrogenations.

## Claims

### Claim 1

An enantiomerically pure bisphosphines of the general formula (I) ##STR11## where R in each case represents a phenyl group which in turn can be substituted by from 1 to 3 substituents from the group OR.sup.1, R.sup.1, nitro, NH.sub.2, NHR.sup.1 or NR.sub.2.sup.1, where R.sup.1 is an alkyl group having up to 6 carbon atoms, or
R is an alkyl group having up to 7 carbon atoms or a cycloalkyl group having from 3 to 7 carbon atoms.

### Claim 2 (depends on 1)

A bisphosphine according to claim 1, where
R in each case represents a phenyl group which in turn can be substituted by from 1 to 3 substituents from the group OR.sup.1, R.sup.1, nitro, NH.sub.2, NHR.sup.1 or NR.sub.1.sup.1, where R.sup.1 is an alkyl group having up to 4 carbon atoms, or
R is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms.

### Claim 3 (depends on 1)

A bisphosphine according to claim 1, where
R represents phenyl.

### Claim 4 (depends on 1)

A process for preparing a bisphosphine of generic formula (I) according to claim 1, said process comprising the steps of:
1. preparing a compound of generic formula (III) ##STR12## wherein R is defined in claim 1, by either:
a)
i) selectively reacting 5-Br-2-Cl anisole with magnesium under Grignard conditions to form the corresponding magnesium bromide Grignard reagent; and
ii) reacting the Grignard reagent formed in step a)i) with phosphorous oxychloride of the generic formula (II) ##STR13## wherein R is defined above, to give a compound of generic formula (III); or
b)
i) selectively reacting 5-Br-2-Cl anisole with magnesium under Grignard conditions to form the magnesium bromide Grignard reagent;
and
ii) reacting the Grignard reagent formed in step b)i) with phosphinic chlorides of generic formula (VI) ##STR14## wherein R is defined above, and subsequently oxidizing the product thus formed to give a compound of generic formula (III);
2. metallating compounds of formula generic (III) in the 6-position followed by reaction with iodine to give a compound of generic formula (IV) ##STR15##
where R is defined above; 3. dimerizing the compounds of generic formula (IV) to give racemic compounds of generic formula (V) ##STR16##
where R is defined above; 4. resolving compounds of formula (V) into their enantiomers by crystallization with enantiomerically pure monocarboxylic or dicarboxylic acids and reducing the enantiomers thus formed to give compounds of generic formula (I).

### Claim 5 (depends on 4)

The process according to claim 4, wherein after converting the 5-Br-2-Cl-anisole into the magnesium bromide Grignard reagent, the Grignard reagent is reacted with phosphorous oxychlorides of generic formula (II) ##STR17## to yield compounds of generic formula (III) the compounds of generic formula (III) are then metallated in the 6-position using a lithium amide and a then subsequently reacted with iodine to give the compounds of generic formula (IV); the compounds of generic formula (IV) are then dimerized by means of an Ullmann coupling to yield racemic compounds of general formula (V) and the phosphine oxides thus obtained are resolved into their enantiomers by crystallization with enantiomerically pure tartaric acids; and these resolved enantiomers are then reduced to the compounds of general formula (I).

### Claim 6 (depends on 1)

A method of using bisphosphines of generic formula (I) according to claim 1 for preparing complexes with a metal of group VIII.