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US 9,174,906 B2Granted
Process for producing optically active secondary alcohol
AssigneesKanto Kagaku Kabushiki Kaisha, National University Corporation Hokkaido University
InventorsTakeaki Katayama, Kunihiko Tsutsumi, Kunihiko Murata, Takeshi Ohkuma, Noriyoshi Arai
Life of this patent
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Abstract
Methods are provided for producing an optically active secondary alcohol at a high optical purity by hydrogenating a substrate carbonyl compound at a high efficiency using as a catalyst a ruthenium complex bearing as a ligand certain optically active diphosphine compound and a readily synthesized amine compound. For example, aromatic ketones and heteroaromatic ketones are reacted with hydrogen and/or a hydrogen donating compound in the presence of the ruthenium complex.
Claims17
A method for producing optically active secondary alcohols, the method comprising:
- reacting a substrate carbonyl compound selected from the group consisting of aromatic ketones and heteroaromatic ketones, and these ketones in which the aromatic ring or heterocycle has a substituent, with hydrogen and/or a hydrogen donating compound in the presence of one or more ruthenium complexes selected by the compounds expressed by following general formula (1):
- RuXYAB (1);
- where,
- X and Y are the same or different from each other and denote a hydrogen atom or an anionic group;
- A denotes an optically active diphosphine expressed by following general formula (2)
- where,
- R1 and R2 are the same or different from each other and denote a C1-20 chained or cyclic hydrocarbon group which may have a substituent;
- R3 and R4 are the same or different from each other and denote a hydrogen atom or a C1-3 hydrocarbon group;
- R5, R6, R7 and R8 are the same or different from each other and denote a hydrocarbon group which may have a substituent;
- and,
- * expresses an asymmetric carbon atom;
- B denotes an amine compound expressed by following general formula (3):
- where,
- each D is independently selected as a carbon atom or nitrogen atom;
- R9, R10 and R11 are the same or different from each other and denote a hydrogen atom or a C1-20 chained or cyclic hydrocarbon group which may have a substituent, and/or, R10 and R11 are connected to each other to form a saturated or unsaturated hydrocarbon ring or heterocycle which may have a substituent;
- each R12 is the same or different from each other and denotes a C1-20 chained or cyclic hydrocarbon group which may have a substituent, and/or, the adjacent R12 are connected to each other to form a saturated or unsaturated hydrocarbon ring or heterocycle which may have a substituent;
- R12 may at least partly be bound to ruthenium as an anionic group X;
- n is an integer ranging from 0 to (4−m) and represents the number of R12 substituents in formula (3);
- and,
- m is an integer ranging from 0 to 4 and represents the number of Ds that are selected as nitrogen atoms in formula (3),
- provided that n is an integer ranging from 2 to 4 when m is 0.
18 more elements
A method for producing optically active secondary alcohols, the method comprising:
- reacting a substrate carbonyl compound selected from the group consisting of aromatic ketones and heteroaromatic ketones, and these ketones in which the aromatic ring or heterocycle has a substituent, with hydrogen and/or a hydrogen donating compound in the presence of one or more complexes selected from the compounds expressed by following general formula (4):
- RuXYA (4);
- where,
- X and Y are the same or different from each other and denote a hydrogen or an anionic group,
- A denotes an optically active diphosphine expressed by following general formula (2):
- where,
- R1 and R2 are the same or different from each other and denotes a C1-20 chained or cyclic hydrocarbon group which may have a substituent;
- R3 and R4 are the same or different from each other and denote a hydrogen atom or a C1-3 hydrocarbon group;
- R5, R6, R7 and R8 are the same or different from each other and denote a hydrocarbon group which may have a substituent;
- * expresses an asymmetric carbon atom;
- and,
- one or more amine compound selected from the compounds expressed by following general formula (3):
- where,
- each D is independently selected as a carbon atom or nitrogen atom;
- R9, R10 and R11 are the same or different from each other, denote a hydrogen atom or a C1-20 chained or cyclic hydrocarbon group which may have a substituent, and/or, R10 and R11 are connected to each other to form a saturated or unsaturated hydrocarbon ring or heterocycle which may have a substituent;
- each R12 is the same or different from each other and denotes a C1-20 chained or cyclic hydrocarbon group which may have a substituent, and/or, the adjacent R12 are connected to each other to form a saturated or unsaturated hydrocarbon ring or heterocycle which may have a substituent;
- R12 may at least partly be bound to ruthenium as an anionic group X;
- n is an integer ranging from 0 to (4−m) and represents the number of R12 substituents in formula (3);
- and,
- m is an integer ranging from 0 to 4 and represents the number of Ds that are selected as nitrogen atoms in formula (3),
- provided that n is an integer ranging from 2 to 4 when m is 0.
18 more elements
Dependencies are inferred from the claim text.