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Catalyst for asymmetric synthesis, ligand for use therein, and process for producing optically active compound through asymmetric synthesis reaction using them achieved

Foreign code F110005599
File No. RX01P32WO
Posted date Sep 9, 2011
Country United States of America
Application number 88453706
Gazette No. 20090156849
Gazette No. 7964743
Date of filing Feb 17, 2006
Gazette Date Jun 18, 2009
Gazette Date Jun 21, 2011
International application number JP2006302850
International publication number WO2006088142
Date of international filing Feb 17, 2006
Date of international publication Aug 24, 2006
Priority data
  • P2005-041116 (Feb 17, 2005) JP
  • 2006WO-JP302850 (Feb 17, 2006) WO
Title Catalyst for asymmetric synthesis, ligand for use therein, and process for producing optically active compound through asymmetric synthesis reaction using them achieved
Abstract (US7964743)
Compounds represented by the following general formula (1a) or (1b).
A complex comprising a center metal of rhodium and a compound represented by the following general formula (1a) or (1b) as a ligand.
A catalyst for optically active beta-substituted carbonyl compound synthesis and catalyst for asymmetric 1, 2 addition reaction being composed of the complex.
A method of production of an optically active beta-aryl compound from an alpha, beta-unsaturated compound and an aryl-boronic acid derivative and method of production of an optically active aryl alcohol compound from an aldehyde compound and aryl boronic acid derivatives using the catalyst.
A complex comprising a center metal of palladium and a compound represented by the following general formula (1a) or (1b) as a ligand.
A catalyst for asymmetric allylic substitution reaction being composed of the complex.
A method of production of an optically active dialkyl (1,3-disubstituted propeny)malonate compound from a 1,3-disubstituted ally acetate compound and a dialkyl malonate and method of production of an optically active allylamine compound from a 1,3-disubstituted ally acetate compound and an amine compound.
The compounds have not only the versatility of being usable in the synthesis of wide-ranging optically active aryl compounds but also the selectivity and reactivity permitting synthesis with high yield within a short period of time under industrially advantageous mild conditions.
Scope of claims [claim1]
1. A compound denoted by general formula (1a) or (1b) below:

(wherein X denotes carbon, oxygen, sulfur, or nitrogen; Y denotes NR10R11 (wherein R10 and R11 each independently denote a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group), OR12 (wherein R12 denotes a substituted or unsubstituted alkyl group, or substituted or unsubstituted aryl group), or SR13 (wherein R13 denotes a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group); n denotes an integer of from 1 to 3; R1 to R8 each independently denote hydrogen, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group).
[claim2]
2. A complex, the core metal of which is rhodium, iridium, or ruthenium, comprising the compound denoted by general formula (1a) or (1b) of claim 1 as ligand.
[claim3]
3. The complex according to claim 2 denoted by general formula (20) below:
M1XmL1pL2q (20)
(wherein M1 denotes rhodium, iridium, or ruthenium; X denotes a halogen, RO (wherein RO denotes a member selected from the group consisting of hydroxy, alkoxy, acetyl acetonate, acetoxy, and trifluoromethane sulfonate), a BF4, ClO4, PF6, B(Ar)4, or SbF6 anion, or hydrogen; m denotes an integer of from 1 to 3; L1 denotes an olefin, eta3-allyl, aryl (Ar) group, amine, carbon monoxide, or acetonitrile; p denotes an integer of from 0 to 3; L2 denotes the compound represented by general formula (1a) or (1b); q denotes the integer 1 or 2; and aryl (Ar) denotes an aromatic ring).
[claim4]
4. A catalyst for synthesizing optically active beta-substituted carbonyl compounds comprising the complexes according to claim 2.
[claim5]
5. A catalyst for asymmetric 1,2-addition reactions comprised of the complexes according to claim 2.
[claim6]
6. A method of manufacturing an optically active beta-substituted carbonyl compound by reacting a substituted or unsubstituted alpha, beta-unsaturated compound and an organic metal reagent, characterized by conducting the reaction in the presence of the complex according to claim 2.
[claim7]
7. The method according to claim 6, wherein the substituent in said alpha, beta-unsaturated compound is a carboxyl group, alkoxycarbonyl group, cyano group, substituted carbamoyl group, acyl group, formyl group, or nitro group.
[claim8]
8. The method according to claim 6, wherein said alpha, beta-unsaturated compound is a compound denoted by general formula (2a) or (2b) below:

(wherein R1, R2, and R3, which may be identical or different, each denote a hydrogen, alkyl group having 1 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms, alkylthio group having 1 to 8 carbon atoms, or amino group optionally having an alkyl group with 1 to 8 carbon atoms; E denotes a carboxyl group, cyano group, carbamoyl group optionally having an alkyl group with 1 to 8 carbon atoms, or nitro group; n denotes an integer of 0 or greater; W and Z, which may be identical or different, each denote -- CH2 -- , .dbd.CH -- , -- O -- , -- S -- , -- NH -- , or .dbd.N -- ; R10 and R11, which may be identical or different, each denote a hydrogen atom, alkyl group having 1 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms, nitro group, cyano group, acyl group having 2 to 8 carbon atoms, alkoxycarbonyl group having 2 to 8 carbon atoms, or amino group optionally having an alkyl group with 1 to 8 carbon atoms, or adjacent R10 and R11 denote general formula (a) below:

(wherein R12 denotes a hydrogen atom, alkyl group having 1 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms, cyano group, halogenated alkyl group, halogen atom, carbamoyl group optionally having an alkyl group with 1 to 8 carbon atoms, acyl group having 2 to 8 carbon atoms, alkoxycarbonyl group having 2 to 8 carbon atoms, or amino group optionally having an alkyl group with 1 to 8 carbon atoms)).
[claim9]
9. The method according to claim 6, wherein said organometallic reagent is a metal-substituted or unsubstituted alkyl, alkenyl, alkynyl, or aryl compound.
[claim10]
10. The method according to claim 6, wherein said organometallic reagent is an organic boronic acid derivative of the compound denoted by general formula (3a), (3b), or (3c):

(wherein Y denotes a hydroxyl group, alkoxy group having 1 to 8 carbon atoms, phenoxy group optionally having an alkyl group with 1 to 8 carbon atoms, cyclohexyloxy group, or group denoted by formula a, b, c, or d (in each of which q denotes an integer of from 1 to 4; r and s each independently denote an integer of from 0 to 5, and Me denotes a methyl group); and R denotes a substituted or unsubstituted alkyl, alkenyl, alkynyl, or aryl group).
[claim11]
11. The method according to claim 6, wherein said optically active beta-substituted carbonyl compound denotes the compound represented by general formula (4) below:

(wherein R1, R2, and R3, which may be identical or different, each denote a hydrogen atom, alkyl group having 1 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms, alkylthio group having 1 to 8 carbon atoms, or amino group optionally having an alkyl group with 1 to 8 carbon atoms; E denotes a carboxyl group, cyano group, carbamoyl group optionally having an alkyl group with 1 to 8 carbon atoms, or nitro group; and R denotes a substituted or unsubstituted alkyl, alkenyl, alkynyl, or aryl group).
[claim12]
12. A method of manufacturing an optically active alcohol compound by reacting an aldehyde compound and an organometallic reagent, characterized by being conducted in the presence of the complex according to claim 2.
[claim13]
13. The method according to claim 12, wherein said aldehyde compound is the compound denoted by general formula (5):
R4CHO (5)
(wherein R4 denotes a substituted or unsubstituted alkyl group or substituted or unsubstituted aryl group).
[claim14]
14. The method according to claim 12, wherein said organometallic reagent is a metal-substituted or unsubstituted alkyl, alkenyl, alkynyl, or aryl group.
[claim15]
15. The method according to claim 12, wherein said organometallic reagent is an organoboronic acid derivative denoted by general formula (3a), (3b), or (3c) below:

(wherein Y denotes a hydroxyl group, alkoxy group having 1 to 8 carbon atoms, phenoxy group optionally having an alkyl group with 1 to 8 carbon atoms, cyclohexyloxy group, or the group denoted by formula a, b, c, or d below (in each of which q denotes an integer of from 1 to 4, r and s each independently denote an integer of from 0 to 5, and Me denotes a methyl group); and R denotes a substituted or unsubstituted alkyl, alkenyl, alkynyl, or aryl group):
[claim16]
16. The method according to claim 12, wherein said optically active alcohol is the compound denoted by general formula (7) below:

(wherein R4 denotes a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group; and R denotes a substituted or unsubstituted alkyl, alkenyl, alkynyl, or aryl group).
[claim17]
17. A complex, the core metal of which is palladium or platinum, comprising the compound denoted by general formula (1a) or (1b) of claim 1 as ligand.
[claim18]
18. The complex according to claim 17, denoted by general formula (21) below:
M2XrL3sL4t (21)
(wherein M2 denotes palladium or platinum; X denotes a halogen, acetate anion, BF4, PF6, ClO4, B(Ar)4, or SbF6 anion; r denotes an integer of from 0 to 2; L3 denotes a triaryl (or alkyl) phosphine, acetonitrile, benzonitrile, dibenzylidene acetone, or eta3-allyl; s denotes an integer of from 0 to 2; L4 denotes the compound according to general formula (1a) or (1b); t denotes 1; and Ar denotes an aromatic ring).
[claim19]
19. A catalyst for an asymmetric allylic substitution reaction, comprising the complex according to claim 17.
[claim20]
20. The catalyst according to claim 19, in which the asymmetric allylic substitution reaction is an asymmetric allylic alkylation reaction.
[claim21]
21. The catalyst according to claim 19, wherein the asymmetric allylic substitution reaction is an asymmetric allylic amination reaction.
[claim22]
22. A method of manufacturing an optically active (1,3-disubstituted propenyl)dialkyl malonate compound by reacting a 1,3-disubstituted allyl acetate compound with a dialkyl malonate, characterized by conducting said reaction in the presence of the complex according to claim 17.
[claim23]
23. The method according to claim 22, wherein said 1,3-disubstituted allyl acetate compound is the compound denoted by general formula (8) below:

(wherein R5 and R6 denote identical substituted or unsubstituted alkyl groups, or substituted or unsubstituted aryl groups; and Ac denotes an acetyl group).
[claim24]
24. The method according to claim 22, wherein said dialkyl malonate is the compound dented by general formula (9) below:

(wherein R7 denotes a substituted or unsubstituted alkyl group).
[claim25]
25. The method according to claim 22, wherein said optically active (1,3-disubstituted propenyl)dialkyl malonate compound is the compound denoted by general formula (10) below:

(wherein R5 and R6 denote identical substituted or unsubstituted alkyl groups or substituted or unsubstituted aryl groups; and R7 denotes a substituted or unsubstituted alkyl group).
[claim26]
26. A method of manufacturing an optically active allylamine compound by reacting a 1,3-disubstituted allyl acetate compound and an amine compound, characterized by conducting said reaction in the presence of the complex according to claim 17.
[claim27]
27. The method according to claim 26, wherein said 1,3-disubstituted allyl acetate compound is the compound denoted by general formula (11) below:

(wherein R5 and R6 denote identical substituted or unsubstituted alkyl groups or substituted or unsubstituted aryl groups; and Ac denotes an acetyl group).
[claim28]
28. The method according to claim 26, wherein said amine compound is the compound denoted by general formula (12) below:

(wherein R8 and R9 each independently denote hydrogen, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, it being permissible for R8 and R9 to form a ring having 3 to 7 carbon atoms).
[claim29]
29. The method according to claim 26, wherein said optically active allylamine compound is the compound denoted by general formula (13) below:

(wherein R5 and R6 denote identical substituted or unsubstituted alkyl groups or substituted or unsubstituted aryl groups; and R8 and R9 each independently denote hydrogen, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, it being permissible for R8 and R9 to form a ring having 3 to 7 carbon atoms).
  • Inventor, and Inventor/Applicant
  • MIYAURA NORIO
  • YAMAMOTO YASUNORI
  • JAPAN SCIENCE AND TECHNOLOGY AGENCY
IPC(International Patent Classification)
U.S. Cl./(Sub)
  • B01J031/18C2
  • B01J031/18C2D
  • C07B053/00
  • C07C029/38
  • C07C045/69
  • C07C067/343
  • C07C209/16
  • C07C231/12
  • C07F009/6571B
  • C07F015/00N5B
  • C07F015/00N6
  • C07F015/00N6B
  • L01J231/34B2D
  • L01J231/34D
  • L01J231/44
  • L01J531/02H4
  • L01J531/82B
  • L01J531/82D
  • L01J531/82J
  • M07B200/07
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