Top > Search of International Patents > Catalytic asymmetric epoxidation

Catalytic asymmetric epoxidation achieved

Foreign code F110005243
File No. B12-01US1
Posted date Aug 29, 2011
Country United States of America
Application number 65689107
Gazette No. 20070203347
Gazette No. 7714167
Date of filing Jan 22, 2007
Gazette Date Aug 30, 2007
Gazette Date May 11, 2010
Priority data
  • 2004US-10762028 (Jan 20, 2004) US
Title Catalytic asymmetric epoxidation achieved
Abstract (US7714167)
The present invention relates to the synthesis of chiral epoxides via a catalytic asymmetric oxidation of olefins.
Additionally, the methodology provides a method of asymmetrically oxidizing sulfides and phosphines.
This asymmetric oxidation employs a catalyst system composed of a metal and a chiral bishydroxamic acid ligand, which, in the presence of a stoichiometric oxidation reagent, serves to asymmetrically oxidize a variety of substrates.
Scope of claims [claim1]
1. A chiral bishydroxamic acid ligand of a structure I:

wherein: R1, R2, R3, R4, R5 and R6 are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, aryl, heteroaryl, and arylalkyl; or wherein R1 and R2, together with the atom to which they are attached, form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, heterocyclyl, and aryl;
or wherein R4 and R5, together with the atom to which they are attached, form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, heterocyclyl, and aryl;
R7, R8, R9, and R10 are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, aryl, heteroaryl, and arylalkyl;
or wherein R7 and R9, together with the atoms to which they are attached, form a substituted or non-substituted ring selected from the group consisting of cycloalkyl and heterocyclyl;
-Z- is selected from the group consisting of -- CO(O) -- and -- S(O)2 -- .
[claim2]
18. A method of performing a catalytic asymmetric oxidation comprising: reacting a substrate with catalytic amounts of a chiral bishydroxamic acid ligand and a metal, in the presence of an oxidation reagent, to produce a chiral oxidation product;
wherein the substrate is selected from the group consisting of sulfide and phosphine;
wherein the chiral bishydroxamic acid ligand is of formula (I):

wherein: R1, R2, R3, R4, R5, and R6 are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, aryl, heteroaryl, and arylalkyl; or wherein R1 and R2, together with the atom to which they are attached, form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, heterocyclyl, and aryl;
or wherein R4 and R5, together with the atom to which they are attached, form a substituted or unsubstituted ring selected from the group consisting of cycloalkyl, heterocyclyl, and aryl;
R7, R8, R9, and R10 are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, aryl, heteroaryl, and arylalkyl;
or wherein R7 and R9, together with the atoms to which they are attached, form a substituted or non-substituted ring selected from the group consisting of cycloalkyl and heterocyclyl;
-Z- is selected from the group consisting of -- CO(O) -- and -- S(O)2 -- or the chiral bishydroxamic acid ligand is of formula (Ib') or (Ic'):
wherein:
R13, R14, R15, R16, R17, and R18 are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, awl, heteroaryl, and arylalkyl;
R19 and R20 are each independently selected from the group consisting of hydrogen, halogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, awl, heteroaryl, and arylalkyl;
R21, R22, R23, and R24 are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, aryl, heteroaryl, and arylalkyl; and
R25 and R26 are each independently selected from the group consisting of hydrogen, halogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, aryl, heteroaryl, and arylalkyl.
[claim3]
2. The ligand of claim 1, wherein R1, R2, R3, R4, R5, and R6 are each independently selected from the group consisting of hydrogen, alkyl, alkyloxy, and alkylamino.
[claim4]
3. The ligand of claim 1, wherein R1, R2, R3, R4, R5, and R6 are each independently selected from the group consisting of cycloalkyl and heterocyclyl.
[claim5]
4. The ligand of claim 1, wherein R1, R2, R3, R4, R5, and R6 are each independently selected from the group consisting of aryl, arylalkyl, heteroaryl, and halogen.
[claim6]
5. The ligand of claim 1, wherein: R1 and R2, together with the atom to which they are attached, form a substituted or unsubstituted ring;
R4 and R5, together with the atom to which they are attached, form a substituted or unsubstituted ring; and
the ring formed by R1 and R2 is identical to the ring formed by R4 and R5.
[claim7]
6. The ligand of claim 1, wherein R7, R8, R9, and R10 are each independently selected from the group consisting of hydrogen, alkyl, alkyloxy, and alkylamino.
[claim8]
7. The ligand of claim 1, wherein R7, R8, R9, and R10 are each independently selected from the group consisting of cycloalkyl and heterocyclyl.
[claim9]
8. The ligand of claim 1, wherein R7, R8, R9, and R10 are each independently selected from the group consisting of awl, arylalkyl, and heteroaryl.
[claim10]
9. The ligand of claim 1, wherein R7 and R9, together with the atoms to which they are attached, form a ring.
[claim11]
10. The ligand of claim 9, wherein R8 and R10 are identical.
[claim12]
11. The ligand of claim 7, wherein R7 and R9, together with the atoms to which they are attached, form a ring.
[claim13]
12. The ligand of claim 11, wherein R8 and R10 are identical.
[claim14]
13. The ligand of claim 1, wherein: R1 and R2 are awl groups;
R3 is hydrogen;
R4 and R5 are awl groups; and
R6 is hydrogen.
[claim15]
14. The ligand of claim 13, wherein: R1 and R2 are identical; and
R4 and R5 are identical.
[claim16]
15. The ligand of claim 14, wherein R1, R2, R4, and R5 are identical.
[claim17]
16. The ligand of claim 1, wherein the chiral bishydroxamic acid ligand (I) is selected from the group consisting of:
[claim18]
17. A chiral bishydroxamic acid ligand, selected from the following formulae:
wherein:
R13, R14, R15, R16, R17, and R18 are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, aryl, heteroaryl, and arylalkyl;
R19 and R20 are each independently selected from the group consisting of hydrogen, halogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, aryl, heteroaryl, and arylalkyl;
R21, R22, R23, and R24 are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, aryl, heteroaryl, and arylalkyl;
R25 and R26 are each independently selected from the group consisting of hydrogen, halogen, alkyl, cycloalkyl, alkoxy, alkylamino, heterocyclyl, aryl, heteroaryl, and arylalkyl.
[claim19]
19. The method of claim 18, wherein the metal is selected from the group consisting of molybdenum (IV), molybdenum (V), and molybdenum (VI).
[claim20]
20. The method of claim 18, wherein the oxidation reagent is an organic hydroperoxide with the following structure (II):
R11 -- O -- OH II
wherein R11 is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and heterocyclyl.
  • Inventor, and Inventor/Applicant
  • YAMAMOTO HISASHI
  • BASAK ARINDRAJIT
  • ZHANG WEI
  • JAPAN SCIENCE AND TECHNOLOGY AGENCY
IPC(International Patent Classification)
Reference ( R and D project ) SORST Selected in Fiscal 2000
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