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US 7,235,696 B2Granted
Chiral diphosphinoterpenes and transition metal complexes thereof
AssigneeLANXESS Deutschland GmbH
InventorsPaul Knochel, Tanasari Bunlaksananusorn, Andrei Gavryushin
Life of this patent
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Abstract
The present invention relates to chiral diphosphinoterpenes and transition metal complexes thereof, to a process for preparing chiral diphosphinoterpenes and oxides thereof, and to transition metal complexes comprising the chiral diphosphinoterpenes. In a further aspect, the invention relates to the use of the chiral diphosphinoterpenes or transition metal complexes thereof in asymmetric syntheses.
Claims9
Process for preparing compounds of the formula (I)
- in which
- *2 and *3 each mark a stereogenic carbon atom which is in R- or S-configuration, although the substituents are arranged in a cisoid manner based on the connecting carbon bond and
- R1, R2, R3 and R4 may each independently be:
- alkyl, arylalkyl or aryl or a heterocyclic radical having a total of 4 to 16 carbon atoms, or R1 and R2 and/or R3 and R4 each together are alkylene or compounds comprising compounds according to formula I and boranes, characterized in that
- in a step A), compounds of the formula (IIa) or (IIb)
- in which *3 has the definitions and areas of preference specified for formula (I)
- are reacted with compounds of the formula (IIIa) or (IIIb)
- Hal-PR1R2 (IIIa)
- Hal-PR3R4 (IIIb)
- to give compounds of the formula (IVa) and (IVb)
- and
- in a step B), the compounds of the formula (IVa) and (IVb), optionally in an organic solvent, are converted by heating to at least 60 C to compounds of the formula (Va) and (Vb)
- and, in a step C), the compounds of the formula (Va) and (Vb) are converted by reacting with a borane and subsequently oxidizing to compounds of the formula (VIa) and (VIb)
- and, in a step D), the compounds of the formula (VIa) and (VIb) are converted by reducing to compounds of the formula (VIIa) and (VIIb)
- and, in a step E), the compounds of the formula (VIIa) and (VIIb) are converted by reacting with compounds of the formula (VIII)
- Hal-O2SR5 (VIII)
- to compounds of the formula (IXa) and (IXb)
- and, in a step F), the compounds of the formula (IX) are converted by reacting with compounds of the formula (Xa) or (Xb)
- HPR3R4 (Xa)
- HPR1R2 (Xb)
- to the compounds of the formula (I), where, in the formulae (IIa), (IIb), (IIIa), (IIIb), (IVa), (IVb), (Va), (Vb), (VIa), (VIb), (VIIa), (VIIb), (IXa), (IXb), (Xa) and (Xb), *2 and *3, R1, R2, R3 and R4 are each defined as has been described in by formula I and
- R5 in the formulae (VIII), (IXa) and (IXb) is alkyl, fluoroalkyl, arylalkyl or aryl and
- Hal in the formulae (IIIa) and (IIIb) and (VIII) is in each case chlorine, bromine or iodine.
20 more elements
A process for the preparation of compounds of formula I
- in which
- *2 and *3 each mark a stereogenic carbon atom which is in R- or S-configuration, although the substituents are arranged in a cisoid manner based on the connecting carbon bond and
- R1, R2, R3 and R4 may each independently be:
- alkyl, arylalkyl or aryl or a heterocyclic radical having a total of 4 to 16 carbon atoms, or R1 and R2 and/or R3 and R4 each together are alkylene, comprising:
- converting compounds according to formula (IXa) and (IXb)
- by reacting the compounds of formula (IX) with compounds of the formula (Xa) or (Xb)
- HPR3R4 (Xa)
- HPR1R2 (Xb)
- wherein *2 and *3, R1, R2, R3 and R4 are each defined with respect to formula I, and
- R5 in formula (IXa) and (IXb) is alkyl, fluoroalkyl, arylalkyl or aryl.
7 more elements
A process for the preparation of compounds of the formula (IVa) and (IVb)
- comprising:
- reacting compounds of formula (IIa) and (IIb)
- with compounds of the formula (IIIa) or (IIIb)
- Hal-PR1R2 (IIIa)
- Hal-PR3R4 (IIIb)
- wherein,
- *3 marks a stereogenic carbon atom which is in R- or S-configuration, although the substituents are arranged in a cisoid manner based on the connecting carbon bond,
- Hal- is in each case chlorine, bromine or iodine, and
- R1, R2, R3 and R4 may each independently be alkyl, arylalkyl or aryl or a heterocyclic radical having a total of 4 to 16 carbon atoms, or R1 and R2 and/or R3 and R4 each together are alkylene.
6 more elements
A process for the preparation of compounds of formula I
- in which
- *2 and *3 each mark a stereogenic carbon atom which is in R- or S-configuration, although the substituents are arranged in a cisoid manner based on the connecting carbon bond and
- R1, R2, R3 and R4 may each independently be:
- alkyl, arylalkyl or aryl or a heterocyclic radical having a total of 4 to 16 carbon atoms, or R1 and R2 and/or R3 and R4 each together are alkylene, comprising:
- a. reacting compounds of the formula (VIIa) and (VIIb)
- with compounds of the formula (VIII)
- Hal-O2SR5 (VIII)
- to form compounds of the formula (IXa) and (IXb)
- and
- b. converting compounds according to formula (IXa) and (IXb) to compounds according to formula (I) by reacting the compounds of formula (IX) with compounds of the formula (Xa) or (Xb)
- HPR3R4 (Xa)
- HPR1R2 (Xb)
- wherein *2 and *3, R1, R2, R3 and R4 are each defined with respect to formula I, Hal- is in each case chlorine, bromine or iodine, and
- R5 in formula (IXa) and (IXb) is alkyl, fluoroalkyl, arylalkyl or aryl.
11 more elements
A process for the preparation of compounds of the formula (Va) and (Vb)
- comprising:
- a. reacting compounds of the formula (IIa) or (IIb)
- with compounds of the formula (IIIa) or (IIIb)
- Hal-PR1R2 (IIIa)
- Hal-PR3R4 (IIIb)
- to give compounds of the formula (IVa) and (IVb)
- and
- b. heating the compounds of the formula (IVa) and (IVb), optionally in an organic solvent, to at least 60 C,
- wherein, *3 marks a stereogenic carbon atom which is in R- or S-configuration, although the substituents are arranged in a cisoid manner based on the connecting carbon bond,
- Hal- is in each case chlorine, bromine or iodine, and
- R1, R2, R3 and R4 may each independently be:
- alkyl, arylalkyl or aryl or a heterocyclic radical having a total of 4 to 16 carbon atoms, or R1 and R2 and/or R3 and R4 each together are alkylene.
9 more elements
A process for the preparation of compounds of formula I
- in which
- *2 and *3 each mark a stereogenic carbon atom which is in R- or S-configuration, although the substituents are arranged in a cisoid manner based on the connecting carbon bond and
- R1, R2, R3 and R4 may each independently be:
- alkyl, arylalkyl or aryl or a heterocyclic radical having a total of 4 to 16 carbon atoms, or R1 and R2 and/or R3 and R4 each together are alkylene, comprising:
- a. reducing the compounds of the formula (VIa) and (VIb)
- to compounds of the formula (VIIa) and (VIIb)
- b. reacting compounds of the formula (VIIa) and (VIIb)
- with compounds of the formula (VIII)
- Hal-O2SR5 (VIII)
- to form compounds of the formula (IXa) and (IXb)
- and
- c. converting compounds according to formula (IXa) and (IXb) to compounds according to formula (I) by reacting the compounds of formula (IX) with compounds of the formula (Xa) or (Xb)
- HPR3R4 (Xa)
- HPR1R2 (Xb)
- where *2 and *3, R1, R2, R3 and R4 are each defined with respect to formula I and
- R5 in formula (IXa) and (IXb) is alkyl, fluoroalkyl, arylalkyl or aryl.
13 more elements
A process for the preparation of compounds of formula I
- in which
- *2 and *3 each mark a stereogenic carbon atom which is in R- or S-configuration, although the substituents are arranged in a cisoid manner based on the connecting carbon bond and
- R1, R2, R3 and R4 may each independently be:
- alkyl, arylalkyl or aryl or a heterocyclic radical having a total of 4 to 16 carbon atoms, or R1 and R2 and/or R3 and R4 each together are alkylene, comprising:
- a. reacting the compounds of formula (Va) and (Vb) with a borane and subsequently oxidizing to compounds of the formula (VIa) and (VIb)
- b. reducing the compounds of the formula (VIa) and (VIb) to compounds of the formula (VIIa) and (VIIb)
- c. reacting compounds of the formula (VIIa) and (VIIb) with compounds of the formula (VIII)
- Hal-O2SR5 (VIII)
- to form compounds of the formula (IXa) and (IXb)
- and
- d. converting compounds according to formula (IXa) and (IXb) to compounds according to formula (I) by reacting the compounds of formula (IX) with compounds of the formula (Xa) or (Xb)
- HPR3R4 (Xa)
- HPR1R2 (Xb)
- wherein *2 and *3, R1, R2, R3 and R4 are each defined with respect to formula I, Hal- is in each case chlorine, bromine or iodine, and
- R5 in formula (IXa) and (IXb) is alkyl, fluoroalkyl, arylalkyl or aryl.
12 more elements
Dependencies are inferred from the claim text.