Hydrogenation of l-sorbose

Patent metadata

Field	Value
Publication number	US-12559446-B2
Application number	US-202117918634-A
Country	US
Kind code	B2
Filing date	Apr 13, 2021
Priority date	Apr 14, 2020
Publication date	Feb 24, 2026
Grant date	Feb 24, 2026

Abstract

The invention relates to a process for L-Iditol by hydrogenating L-Sorbose. Further, the invention also relates to a use of a transition metal complex as hydrogenation catalyst for L-Sorbose. The invention relates to a process for the preparation of L-Iditol comprising at least one reaction step, in which a composition comprising L-Sorbose and hydrogen is reacted in the presence of a transition metal catalyst complex in a homogeneous solution, wherein the transition metal catalyst complex comprises at least one chiral ligand containing at least one phosphorus atom, which is capable of coordinating to the transition metal, and wherein the transition metal is selected from metals of groups 8, 9 and 10 of the periodic table of the elements according to IUPAC. The invention further relates to a use of a transition metal complex as defined above and below as hydrogenation catalyst for compositions comprising L-Iditol or mixtures thereof.

First claim

The invention claimed is:

1 . A process for the preparation of L-Iditol comprising at least one reaction step, in which a composition comprising L-Sorbose and hydrogen is reacted in the presence of a transition metal catalyst complex in homogeneous solution, wherein the transition metal catalyst complex comprises at least one chiral ligand containing at least one phosphorus atom, which is capable of coordinating to the transition metal, and wherein the transition metal is selected from metals of groups 8, 9 and 10 of the periodic table of the elements according to IUPAC; and wherein the chiral ligand is selected from compounds of formula (I)

wherein
R A , R B , R C and R D are independently from each other alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, wherein the alkyl radicals may carry 1, 2, 3, 4 or 5 substituents selected from cycloalkyl, heterocycloalkyl, aryl, hetaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy, hetaryloxy, hydroxy, mercapto, polyalkylene oxide, polyalkyleneimine, carboxyl, SO 3 H, sulfonate, NE 1 E 2 , NE 1 E 2 E 3+ X − , halogen, nitro, formyl, acyl and cyano, wherein E 1 , E 2 and E 3 are the same or different and are selected from hydrogen, alkyl, cycloalkyl and aryl, and X − is an anion equivalent,
and wherein the cycloalkyl, heterocycloalkyl, aryl and hetaryl radicals R A , R B , R C and R D may carry 1, 2, 3, 4 or 5 substituents selected from alkyl and the substituents mentioned for the alkyl radicals R A , R B , R C and R D before, or

R A and R B and/or R C and R D together with the P atom and, if present, the groups X 1 , X 2 , X 5 and X 6 to which they are bound, are a 5- to 8-membered heterocycle, which is optionally fused with one, two or three groups selected from cycloalkyl, heterocycloalkyl, aryl and heteroaryl, wherein the heterocycle and, if present, the fused-on groups independently from each other may each carry 1, 2, 3 or 4 substituents selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, hydroxy, mercapto, polyalkylene oxide, polyalkyleneimine, alkoxy, halogen, carboxyl, SO 3 H, sulfonate, NE 4 E 5 NE 4 E 5 E 6+ X − nitro, alkoxycarbonyl, formyl, acyl and cyano, wherein E 4 , E 5 and E 6 are the same or different and are selected from hydrogen, alkyl, cycloalkyl and aryl, and X − is an anion equivalent,
X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 and X 9 are independently from each other O, S, CR x R y , SiR x R y or NR z , wherein R x , R y and R z are independently from each other hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
Y is divalent bridging group, which contains carbon atoms,
a, b, c, d, e and f are independently from each other 0 or 1,
provided that the ligand bears at least one chiral moiety.

2 . The process according to claim 1 , wherein the transition metal is selected from the group consisting of ruthenium, rhenium, iridium, nickel, platinum and palladium and combinations thereof.

3 . The process according to claim 1 , wherein the transition metal is ruthenium.

4 . The process according to claim 1 , wherein the chiral ligand is
selected from compounds of formulae (II) or (III)

wherein
R A , R B , R C and R D have one of the meanings as defined in claim 1 ,
Y is a divalent bridging group, which contains carbon atoms,
Q 1 and Q 2 are independently from each other a divalent bridging group of the formula (IV),

wherein

# denotes the binding sites to the remainder of the molecule,
R e1 , R e2 , R e3 , R e4 , R e5 , R e6 , R e7 and R e8 are independently from each other hydrogen, in each case unsubstituted or substituted alkyl, alkoxy, cycloalkyl, cycloalkoxy, heterocycloalkyl, heterocycloalkoxy, aryl, aryloxy, hetaryl, hetaryloxy, halogen, hydroxy, mercapto, cyano, nitro, formyl, acyl, carboxy, carboxylate, alkylcarbonyloxy, carbamoyl, SO 3 H, sulfonate or NE 7 E 8 , wherein E 7 and E 8 are the same or different and are selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl and hetaryl,
wherein two adjacent radicals R e1 to R e8 together with the carbon atoms of the benzene ring to which they are bound may also be a condensed ring system with 1, 2 or 3 further rings, and

A 1 is a single bond, O, S, NR a31 , SiR a32 R a33 or C 1 -C 4 -alkylene, wherein C 1 -C 4 -alkylene may have a double bond and/or wherein C 1 -C 4 -alkylene may be substituted with alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, and/or wherein C 1 -C 4 -alkylene may be interrupted by O, S, NR a31 or SiR a32 R a33 wherein R a31 , R a32 and R a33 are independently from each other hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.

5 . The process according to claim 4 , wherein the chiral ligand is selected from compounds of formulae (I) or (II), wherein
R A , R B , R C and R D are independently from each other alkyl, aryl or heteroaryl, wherein the alkyl radical may carry 1, 2, 3, 4 or 5 substituents selected from alkoxy, NE 1 E 2 , NE 1 E 2 E 3+ X − , wherein E 1 , E 2 and E 3 are the same or different and are selected from hydrogen or alkyl, and X − is an anion equivalent, and the aryl or heteroaryl radicals may carry 1, 2, 3, 4 or 5 substituents selected from alkyl, and the substituents mentioned for the alkyl radicals, Y is a divalent bridging group, which contains carbon atoms, and a, b, c, d, e and f are 0, with the proviso that at least one of the P atoms is chiral, and/or the ligand of the formulae (I) or (II) has axial chirality.

6 . The process according to claim 4 , wherein the ligand of formulae (I), (II) or (III) has axial chirality.

7 . The process according to claim 1 , wherein the asymmetric divalent bridging group Y has the formulae (V) or (VI)

wherein
# denotes the binding sites to the remainder of the molecule,
R I , R I′ , R II , R II′ , R III , R III′ , R IV , R IV′ , R V , R V′ , R VI , R VI′ , R VII , R VIII′ , R VIII , R IX , R X , R XI and R XII are each, independently from each other, hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, hydroxy, thiol, polyalkylene oxide, polyalkylenimine, alkoxy, halogen, SO 3 H, sulfonate, NE 1 E 2 , alkylene-NE 1 E 2 , nitro, alkoxycarbonyl, carboxyl, acyl or cyano, wherein E 1 and E 2 are identical or different and are selected from hydrogen, alkyl, cycloalkyl and aryl, wherein two adjacent radicals R I′ , R II′ , R III′ , R IV′ , R V′ , R VI′ , R VIII′ together with the carbon atoms of the benzene ring to which they are bound may also be a condensed ring system with 1, 2 or 3 further rings, wherein the ring atoms are selected from carbon, oxygen and sulfur, and wherein each of the rings may carry 1, 2 or 3 substituents selected from halogen C 1 -C 4 -alkyl and C 1 -C 4 -alkoxy, wherein two radicals R IV′ and R V′ together with the carbon atoms of the two benzene rings to which they are bound may also be a condensed ring system, wherein the ring atoms are selected from carbon, oxygen and sulfur, and wherein each of the rings may carry 1, 2 or 3 substituents selected from halogen C 1 -C 4 -alkyl and C 1 -C 4 -alkoxy.

8 . The process according to claim 1 , where the transition metal catalyst complex comprises at least one ligand selected from th

Assignees

• Basf Se

Inventors

• Schaub Thomas
• Kindler Alois
• Mader Steffen
• Hashmi A Stephen K
• Tindall Daniel James

Classifications

• C07B2200/07

  Optical isomers · CPC title

• B01J2531/821

  Ruthenium · CPC title

• B01J2231/641

  Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes · CPC title

• B01J31/2452

  with more than one complexing phosphine-P atom · CPC title

• Y02P20/55

  Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups · CPC title