Phosphoramide compound, method for producing the same, ligand, complex, catalyst and method for producing optically active alcohol
View Patent ↗Disclosed is a method for highly efficiently obtaining an optically active alcohol from a carbonyl compound highly enantioselectively. Also disclosed is a ligand used in such a method. Specifically, an optically active alcohol is obtained by reacting a carbonyl compound and an organozinc compound by using a ligand (L) shown below.
1. A method for producing an optically active alcohol, comprising:
reacting a carbonyl compound with an organozinc compound in the presence of a phosphoramide compound,
wherein the carbonyl compound is one of an aldehyde compound and a ketone compound,
wherein the organozinc compound comprises a compound represented by general formula (11) or compounds represented by general formulae (12) and (13),
ZnR 10 R 11 (11)
ZnR 12 R 13 (12)
ZnR 14 R 15 (13)
wherein
R 10 and R 11 independently are monovalent hydrocarbon groups, and at least one of R 10 and R 11 is an alkyl group, alkenyl group or alkynyl group;
R 12 and R 13 independently are aryl group, arylalkyl group or arylalkenyl group; and
R 14 and R 15 independently are alkyl group, alkenyl group or alkynyl group, and the phosphoramide compound is represented by general formula (1) or (1′)
wherein
R 1 is an alkyl group having 1 to 8 carbon atoms, a phenyl group or an optionally substituted benzyl group;
R 2 and R 3 independently are a phenyl group, a naphthyl group, a cyclohexyl group or an aryl group having 6 to 15 carbon atoms that may have a substituent;
R 4 and R 5 independently are an alkyl group having 1 to 8 carbon atoms or may be bonded together to form a five-to-eight membered saturated ring with a nitrogen atom to which R 4 and R 5 are attached, where the ring may have a hetero atom in the ring;
X is an oxygen atom; and
B is a methylene group or carbonyl group.
2. The method for producing an optically active alcohol according to claim 1 , wherein said phosphoramide compound is added in an amount in the range from 0.1% to 20% by mol based on said carbonyl compound.
3. The method for producing an optically active alcohol according to claim 1 , wherein said carbonyl compound is a ketone compound represented by general formula (14) or (15):
wherein
R 16 is a monovalent hydrocarbon group having three or more carbon atoms;
R 17 is a monovalent hydrocarbon group different from R 16 ; n is an integer of two or more; and
the aromatic ring of the general formula (15) may have a substituent.
4. The method for producing an optically active alcohol according to claim 1 , wherein an equivalent ratio of said organozinc compound represented by general formula (12) to said organozinc compound represented by general formula (13) is 1:(1 to 5).
5. A method for producing an optically active alcohol, comprising:
reacting a carbonyl compound with an organozinc compound in the presence of a ligand,
wherein the carbonyl compound is one of an aldehyde compound and a ketone compound,
wherein the organozinc compound comprises a compound represented by general formula (11) or compounds represented by general formulae (12) and (13),
ZnR 10 R 11 (11)
ZnR 12 R 13 (12)
ZnR 14 R 15 (13)
wherein
R 10 and R 11 independently are monovalent hydrocarbon groups, and at least one of R 10 and R 11 is an alkyl group, alkenyl group or alkynyl group;
R 12 and R 13 independently are aryl group, arylalkyl group or arylalkenyl group; and
R 14 and R 15 independently are alkyl group, alkenyl group or alkynyl group, and the ligand is represented by general formula (8a), (8b), (9a) or (9b):
wherein
R 1 to R 3 and R 7 independently are monovalent hydrocarbon groups;
R 2 and R 3 are each bound to a phosphorus atom directly or via an atom other than carbon atom;
R 6 is a hydrogen atom or a monovalent hydrocarbon group;
X is an oxygen atom or sulfur atom; and
B is a methylene group or carbonyl group.
6. The method according to claim 5 ,
wherein said reacting is performed in the presence of a complex comprising the ligand and a zinc atom.
7. The method according to claim 6 , for
wherein said reacting is performed in the presence of a catalyst comprising the complex.
8. The method according to claim 1 , wherein the reacting is performed in the presence of a complex or a catalyst comprising the complex, and the complex comprises the phosphoramide compound and a zinc atom.
9. The method according to claim 1 , wherein the carbonyl compound is an aldehyde compound.
10. The method according to claim 1 , wherein the carbonyl compound is a ketone compound.
11. The method according to claim 1 , wherein R 2 and R 3 independently are an alkoxyphenyl group or a halogenated alkylphenyl group.
12. The method according to claim 5 , wherein the carbonyl compound is an aldehyde compound.
13. The method according to claim 5 , wherein the carbonyl compound is a ketone compound.