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Catalytic asymmetric epoxidation 実績あり

外国特許コード F110005243
整理番号 B12-01US1
掲載日 2011年8月29日
出願国 アメリカ合衆国
出願番号 65689107
公報番号 20070203347
公報番号 7714167
出願日 平成19年1月22日(2007.1.22)
公報発行日 平成19年8月30日(2007.8.30)
公報発行日 平成22年5月11日(2010.5.11)
優先権データ
  • 2004US-10762028 (2004.1.20) US
発明の名称 (英語) Catalytic asymmetric epoxidation 実績あり
発明の概要(英語) (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.
特許請求の範囲(英語) [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.
  • 発明者/出願人(英語)
  • YAMAMOTO HISASHI
  • BASAK ARINDRAJIT
  • ZHANG WEI
  • JAPAN SCIENCE AND TECHNOLOGY AGENCY
国際特許分類(IPC)
米国特許分類/主・副
  • B01J031/00R
  • B01J031/02B
  • B01J031/22B2B
  • C07D301/14
  • C07D303/14
参考情報 (研究プロジェクト等) SORST Selected in Fiscal 2000
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