Method for converting hydroxyl group of alcohol

Patent metadata

Field	Value
Publication number	US-11407703-B2
Application number	US-201917051261-A
Country	US
Kind code	B2
Filing date	May 8, 2019
Priority date	May 9, 2018
Publication date	Aug 9, 2022
Grant date	Aug 9, 2022

Abstract

The present invention relates to: a method for converting a hydroxyl group of an alcohol; and a catalyst which makes the method possible. A method for converting a hydroxyl group of an alcohol according to the present invention is characterized by producing a compound represented by CH(R1)(R2)Nu (wherein R1, R2 and Nu are as defined below) by reacting an alcohol represented by CH(R1)(R2)OH (wherein each of R1 and R2 represents a hydrogen atom, an optionally substituted alkyl group, or the like) and a compound having an active proton, which is represented by H-Nu (wherein Nu represents a group represented by —CHX1-EWG1 or —NR3R4; X1 represents a hydrogen atom or the like; EWG1 represents an electron-withdrawing group; and each of R3 and R4 represents a hydrogen atom, an optionally substituted alkyl group, or the like), with each other in the presence of a complex of a group 7-11 metal of the periodic table and at least one solid base that is selected from the group consisting of layered double hydroxides, composite oxides and calcium hydroxide.

First claim

The invention claimed is:

1. A method for converting a hydroxyl group of an alcohol, comprising reacting:
in the presence of a metal complex of Groups 7 to 11 in the periodic table and at least one solid base selected from the group consisting of a layered double hydroxide, a composite oxide and calcium hydroxide;
an alcohol represented by the following general formula (1):

wherein:
R 1 and R 2 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted heterocyclyl group or an optionally substituted aralkyl group, where at least one of R 1 and R 2 may have a hydroxyl group as a substituent, and/or R 1 and R 2 may be joined together to form a ring; with a compound having an active proton represented by the following general formula (2):
[Formula 2]
H-Nu  (2),

wherein:
Nu is a group represented by —CHX 1 -EWG 1 or —NR 3 R 4 , where X 1 is a hydrogen atom or a substituent, EWG 1 is an electron-withdrawing group, and R 3 and R 4 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted heterocyclyl group or an optionally substituted aralkyl group, where R 3 and R 4 may be joined together to form a ring; or
when R 1 in general formula (1) is attached to X 1 or R 3 in Nu in general formula (2) such that the alcohol and the compound having an active proton form a single molecule, the reaction occurs within the molecule;
to produce a compound represented by the following general formula (3):

wherein:
R 1 , R 2 and Nu are as defined above, where R 1 and X 1 or R 3 in Nu may be joined together to form a ring, and wherein the solid base is (a) a layered double hydroxide or (b) a composite oxide comprising two or more metal elements, at least one of which is a metal element selected from the group consisting of aluminum, magnesium and calcium.

2. The method for converting a hydroxyl group of claim 1 , wherein the solid base is a layered double hydroxide.

3. The method for converting a hydroxyl group of claim 2 , wherein the layered double hydroxide is a hydrotalcite-type compound.

4. The method for converting a hydroxyl group of claim 1 , wherein the solid base is a composite oxide comprising two or more metal elements, at least one of which is a metal element selected from the group consisting of aluminum, magnesium and calcium.

5. The method for converting a hydroxyl group of claim 1 , wherein the compound having an active proton represented by general formula (2) is a carbonyl compound represented by the following general formula (2-1):

wherein:
X 1 is as defined above, and
R 5 is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted aryl group, an optionally substituted heterocyclyl group, an optionally substituted aralkyl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, an optionally substituted amino group or an optionally substituted carbonyl group,
where X 1 and R 5 may be joined together to form a ring.

6. The method for converting a hydroxyl group of claim 1 , wherein the metal complex of Groups 7 to 11 in the periodic table is an iridium complex or a ruthenium complex.

7. The method for converting a hydroxyl group of claim 6 , wherein the iridium complex is:
a compound represented by the following general formula (4-1) or a dimer thereof:

wherein:
Y 1 is an optionally substituted cyclopentadienyl group or an optionally substituted indenyl group,
Z 1 is a hydrido or anionic group,
A 1 is an optionally substituted aryl group, an optionally substituted heterocyclyl group or an optionally substituted carbonyl group, where A 1 may partially coordinate to the iridium atom,
X 4 , X 5 , X 6 , X 7 and X 8 are each independently a hydrogen atom or a substituent,
where X 4 and X 5 , X 5 and X 6 , X 6 and X 7 as well as X 7 and X 8 may each be joined together to form a ring, and/or Y 1 and A 1 as well as Y 1 and X 4 may each be joined together to form a ring, and
m is 1 or 2, and n is 1 or 0, provided that n is 1 when m is 1, and n is 0 when m is 2; or
a compound represented by the following general formula (4-2):

wherein:
Y 1 , Z 1 , X 4 , X 5 , X 6 , X 7 and X 8 are as defined above.

8. The method for converting a hydroxyl group of claim 6 , wherein the iridium complex is formed within the reaction system by mixing an iridium compound represented by the following general formula (5-1) or a dimer thereof:
[Y 1 IrZ 1 2 ]  (5-1),

wherein:
Y 1 is an optionally substituted cyclopentadienyl group or an optionally substituted indenyl group, and
Z 1 is a hydrido or anionic group; with
an anilide represented by the following general formula (6-1):

wherein:
A 1 is an optionally substituted aryl group, an optionally substituted heterocyclyl group or an optionally substituted carbonyl group, and
X 4 , X 5 , X 6 , X 7 and X 8 are each independently a hydrogen atom or a substituent,
where X 4 and X 5 , X 5 and X 6 , X 6 and X 7 as well as X 7 and X 8 may each be joined together to form a ring; or with
an anilide represented by the following general formula (6-2):

wherein:
X 4 , X 5 , X 6 , X 7 and X 8 are as defined above.

9. The method for converting a hydroxyl group of claim 6 , wherein the ruthenium complex is:
a compound represented by the following general formula (4-3) or a dimer thereof:

wherein:
Y 2 an optionally substituted arene,
Z 1 is a hydrido or anionic group,
A 1 is an optionally substituted aryl group, an optionally substituted heterocyclyl group or an optionally substituted carbonyl group, where A 1 may partially coordinate to the ruthenium atom,
X 4 , X 5 , X 6 , X 7 and X 8 are each independently a hydrogen atom or a substituent,
where X 4 and X 5 , X 5 and X 6 , X 6 and X 7 as well as X 7 and X 8 may each be joined together to form a ring, and/or Y 1 and A 1 as well as Y 1 and X 4 may each be joined together to form a ring, and
m is 1 or 2, and n is 1 or 0, provided that n is 1 when m is 1, and n is 0 when m is 2; or
a compound represented by the following general formula (4-4):

wherein:
Y 2 , Z 1 , X 4 , X 5 , X 6 , X 7 and X 8 are as defined above.

10. The method for converting a hydroxyl group of claim 6 , wherein the ruthenium complex is formed within the reaction system by mixing a ruthenium compound represented by the following general formula (5-3) or a dimer thereof:
[Y 2 RuZ 1 2 ]  (5-3),

wherein:
Y 2 is an optionally substituted arene, and
Z 1

Assignees

• Takasago Perfumery Co Ltd

Inventors

• Shimizu Hideo
• Hori Kiyoto
• Maeda Hironori

Classifications

• C07C49/12

  Ketones containing more than one keto group · CPC title

• C07C45/71 Primary

  being hydroxy groups · CPC title

• B01J31/22

  Organic complexes · CPC title

• C07C49/784

  with all keto groups bound to a non-condensed ring · CPC title

• C07F15/0046

  Ruthenium compounds · CPC title