Chiral phosphoramidimidates and derivatives thereof

• US 11,084,834 B2
• Filed: 08/31/2016
• Issued: 08/10/2021
• Est. Priority Date: 09/01/2015
• Status: Active Grant

• Current Assignee: Studiengesellschaft Kohle Ggmbh
• Original Assignee: Studiengesellschaft Kohle MBH
• Inventors: List, Benjamin, Kaib, Philip Stephan Joseph, Schreyer, Lucas, Lee, Sunggi, Properzi, Roberta, Liu, Luping
• Primary Examiner(s): Bonaparte, Amy C
• Application Number:
  US15/756,136
• Publication Number:
  US 20180339999A1
• Time in Patent Office: 1,805 Days
• Field of Search: None
• CPC Class Codes: C07B 53/00 Asymmetric syntheses
• CPC Class Codes: C07F 9/22 Amides of acids of phosphorus
• CPC Class Codes: C07F 9/24 Esteramides
• CPC Class Codes: C07F 9/242 of hydroxyaryl compounds
• CPC Class Codes: C07F 9/2495 containing the structure P(=X)n-N-P (X = O, S, Se; n = 0, 1)
• CPC Class Codes: C07F 9/44 Amides thereof
• CPC Class Codes: C07F 9/4419 Amides of aromatic acids (P-C aromatic linkage)
• CPC Class Codes: C07F 9/6564 having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
• CPC Class Codes: C07F 9/657154 Cyclic esteramides of oxyacids of phosphorus
• CPC Class Codes: C07F 9/6578 having phosphorus and sulfur atoms with or without oxygen atoms, as ring hetero atoms
• CPC Class Codes: C07F 9/65848 Cyclic amide derivatives of acids of phosphorus, in which two nitrogen atoms belong to the ring
• CPC Class Codes: C07F 9/6587 having two phosphorus atoms as ring hetero atoms in the same ring

Abstract

The present invention relates to chiral phosphoramidimidates, their salts and metal complexes as well as derivatives thereof and their use as catalysts.

Claims

1. A chiral phosphoramidimidate having the general formula (I):

2. A chiral phosphoramidimidate according to claim 1, wherein in formula (I), Z¹ to Z⁴ independently represent O, S or NR^N, n is 1, and X, R¹ to R⁴, R^N as well as W are as defined in claim 1, as represented by formula (II):

3. A chiral phosphoramidimidate according to claim 1, wherein at least one moiety

4. A chiral phosphoramidimidate according to claim 1, which has the formula (IIIa):

5. A chiral phosphoramidimidate according to claim 1, wherein, in formula (I), Z¹ to Z⁴ represent O, and R¹ to R⁴, X as well as W are as defined in claim 1, and n=1, said phosphoramidimidate having the formula (IIIb):

6. A chiral phosphoramidimidate according to claim 1, wherein (R¹, R², Z¹_n and Z²_n) and (R³, R⁴, Z³_n and Z⁴_n), respectively are as defined in claim 1 and each form a ring structure which may be the same or different and is derived from a bridged, optionally dimeric, aromatic structure selected from biphenyl optionally substituted, BINOL, TADDOL, VAPOL, SPINOL, 1,1′

-binaphthalene, 1,1′

-bianthracene, 1,1-biphenanthrene, or a partially arene-hydrogenated form of said aromatic ring structures including 8H-BINOL, each of said ring systems optionally being substituted by one or more substituents which may be the same or different on each position and are each selected from hydrogen, heterosubstituents, C₁ to C₂₀ straight chain, branched chain or cyclic aliphatic hydrocarbon, optionally having one or more unsaturated bonds, C₃-C₈-heterocycloalkyl, C₆ to C₂₀ aromatic hydrocarbon or a partially arene-hydrogenated form thereof, aryl-(C₁-C₆)-alkyl, or heteroaryl-(C₁-C₆)-alkyl each said aliphatic hydrocarbon, heterocycloalkyl, aromatic hydrocarbon or partially arene-hydrogenated form thereof, arylalkyl, or heteroaryl-alkyl optionally being substituted by one or more groups selected from C₁ to C₂₀ straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having one or more unsaturated bonds, C₃-C₈-heterocycloalkyl, C₆ to C₂₀ aromatic hydrocarbons and partially arene-hydrogenated forms thereof, aryl-(C₁-C₆)-alkyl, heteroaryl-(C₁-C₆)-alkyl, or a heterosubstituent,

wherein n, R^N, X and W are as defined in claim 1,

or a tautomeric and/or ionic form thereof,

wherein the ring structure formed by (R¹, R², Z¹ and Z²) and (R³, R⁴, Z³ and Z⁴) may be the same or different and is chiral.

7. A chiral phosphoramidimidate according to claim 6, wherein the compound of formula (I) has the formula (IV):

8. A chiral phosphoramidimidate according to claim 1, wherein at least one of said ring structures optionally formed by (R¹, R², Z¹ and Z²) and (R³, R⁴, Z³ and Z⁴) respectively is chiral.

9. A chiral phosphoramidimidate according to claim 1, wherein the ring structures optionally formed by (R¹, R², Z¹ and Z²) and (R³, R⁴, Z³ and Z⁴), respectively, are identical.

10. A chiral phosphoramidimidate according to claim 1, which has the following formula (IVa):

11. A chiral phosphoramidimidate according to claim 1, which has the following formula (IVb):

12. A chiral phosphoramidimidate according to claim 1, wherein W is hydrogen.

13. Method of using a chiral phosphoramidimidate of the formula (I) as defined in claim 1 wherein W is H as a chiral Brø

nsted acid catalyst in organic synthesis.

14. Method of using a chiral phosphoramidimidate of the formula (I) as defined in claim 1 wherein W is a metal or the phosphoramidimidate of formula (I) is anionic as a chiral anion in phase-transfer catalysis, or as chiral anion for organic salts, metal salts or metal complexes as catalysts.

15. Method of using a chiral phosphoramidimidate of the formula (I) as defined in claim 1 as a chiral catalyst in a synthetic reaction in organic synthesis, wherein the synthetic reaction is selected from aldol reactions, vinylogous aldol reactions, Mukaiyama aldol reactions, vinylogous Mukaiyama aldol reactions, Mukaiyama-Michael reactions, Michael additions, Mannich reactions, TMSCN additions onto aldehydes, TMSCN additions onto ketones, TMSCN additions onto imines, esterifications, etherifications, pinacol rearrangements, acetalizations, transacetalization, spiroacetalization, cycloadditions, hydroaminations, hydroalkoxylation, hydrations, haloalkoxylation, haloamination, olefin activations in general including ene-reactions and Prins reactions, Friedel-Crafts reactions, epoxide openings, Ritter reactions, nucleophilic substitutions of alcohols, asymmetric ring openings, asymmetric reductions, transfer hydrogenations, alkyne additions, imine additions, Strecker reactions, allylations, propargylations, reductions, epoxidations, olefin metathesis, isomerizations, Diels-Alder reactions, hetero-Diels-Alder reactions, aminalizations, iminium catalysis and enamine catalysis.

18. Process for preparing a chiral phosphoramidimidate of the general formula (I) according to claim 1, said process comprising the steps of:

(a) reacting a compound of the general formulae (V) with a compound of the formula (VI) in the presence of a basic compound in an organic solvent to yield a compound of the formula (VII) as follows;

19. Process for preparing a chiral phosphoramidimidate of the general formula (I) according to claim 1, said process comprising the step of:

reacting a compound of the general formulae (IX) with a compound of the formula (X) in the presence of a basic compound in an organic solvent to yield a compound of the formula (I) as follows;

20. Process for preparing a chiral phosphoramidimidate of the general formula (I) according to claim 1, said process comprising the step of:

reacting a compound of the general formulae (XI) with a compound of the formula (XII) in an organic solvent to yield a compound of the formula (I) as follows;

16. A chiral phosphoramidimidate having the general formula (I):

17. A chiral phosphoramidimidate having the general formula (I):