US4471130A
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Method for asymmetric epoxidation
Assignee: Leland Stanford Junior University
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Filing: 1981-07-27
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Granted: 1984-09-11
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Expires: 2001-07-27
Abstract
Abstract Methods and compositions are provided for asymmetrically donating an oxygen atom to a pair of electrons to produce an asymmetric product. Specifically, a metal alkoxide is used as a catalyst, where the metal has a coordination number of at least four, and at least one, usually two, of the alkoxide groups bonded to the metal are bonded to asymmetric carbon atoms. The metal catalyst is employed in conjunction with a hydroperoxide and an alkanol having a functionality with a pair of electrons capable of accepting an oxygen atom. The resulting product is enriched in one enantiomer due to the enantioselective introduction of an asymmetric center or an enhanced rate of reaction of one of the enantiomers of a chiral alkanol.
Inventors
- 👤 Tsutomu Katsuki
- 👤 Karl B. Sharpless
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 00:09
CPC Classifications
C; C07; C07D; C07D301/00; C07D301/02; C07D301/03; C07D301/19; B; B01; B01J; B01J31/00; B01J31/02; B01J31/0201; B01J31/0211; B01J31/0212; C07D303/00; C07D303/02; C07D303/04; C07D303/12; C07D303/14; C07D303/48; B01J2231/00; B01J2231/70; B01J2231/72
Claims Analysis
Total Claims: 14
Claim 1
Independent Claim
80 words
A method for asymmetrically epoxidizing a carbinol compound having an ethylene group from 0 to 1 carbon atoms from said carbinol; said method comprising: combining in an inert dry medium under mild conditions a metal alkoxide catalyst wherein said metal is titanium or tantalum and has a coordination number of at least 4 and wherein one of said alkoxide groups is optically active; said carbinol compound; and a hydroperoxide; wherein said ethylenic bond is asymmetrically oxidized to form an epoxide.
Claim 2
Independent Claim
80 words
A method for asymmetrically epoxidizing a carbinol compound having an ethylene group from 0 to 1 carbon atoms from said carbinol; said method comprising: combining in an inert dry medium under mild conditions a metal alkoxide catalyst wherein said metal is titanium or tantalum and has a coordination number of at least 4 and wherein one of said alkoxide groups is optically active; said carbinol compound; and a hydroperoxide; wherein said ethylenic bond is asymmetrically oxidized to form an epoxide.
Claim 3
Dependent Claim
12 words
A method according to claim 1, wherein said inert medium is halocarbon.
Claim 4
Dependent Claim
25 words
A method according to claim 1, wherein said metal alkoxide catalyst includes at least one glycol, wherein each of the carbinol carbon atoms are asymmetric.
Claim 5
Independent Claim
20 words
A method according to claims 1, 2 or 3, wherein said mild conditions include a temperature below about 80° C.
Claim 6
Dependent Claim
22 words
A method according to claim 1, wherein said catalyst has as a unit formula: one titanium, two alkoxides, and one tartrate derivative.
Claim 7
Independent Claim
118 words
A method for asymmetrically transferring an oxygen atom to a carbinol compound having a functionality characterized by (1) having a site of ethylenic unsaturation; and (2) said ethylenic unsaturation is separated from said carbinol by from 0 to 1 atoms; said method comprising: combining in an inert dry medium under mild conditions: (1) a catalyst comprising as a unit formula one atom of tetravalent titanium, two alkoxide groups and one glycol, wherein the carbinol carbon atoms of said glycol are separated by from 0 to 1 atoms and are asymmetric at each of said carbinol carbon atoms; (2) said carbinol compound; and (3) a hydroperoxide, whereby said carbinol compound is asymmetrically oxidized to provide an optically active epoxide.
Claim 8
Independent Claim
118 words
A method for asymmetrically transferring an oxygen atom to a carbinol compound having a functionality characterized by (1) having a site of ethylenic unsaturation; and (2) said ethylenic unsaturation is separated from said carbinol by from 0 to 1 atoms; said method comprising: combining in an inert dry medium under mild conditions: (1) a catalyst comprising as a unit formula one atom of tetravalent titanium, two alkoxide groups and one glycol, wherein the carbinol carbon atoms of said glycol are separated by from 0 to 1 atoms and are asymmetric at each of said carbinol carbon atoms; (2) said carbinol compound; and (3) a hydroperoxide, whereby said carbinol compound is asymmetrically oxidized to provide an optically active epoxide.
Claim 9
Dependent Claim
12 words
A method according to claim 6, wherein said double bond is allylic.
Claim 10
Dependent Claim
29 words
A method according to claim 6, wherein said catalyst is prepared by combining titanium tetraalkoxide and said glycol in an inert medium, and distilling off the alcohol which forms.
Claim 11
Dependent Claim
19 words
A method according to claim 6, wherein said glycol is a tartrate other than the acid or its salts.
Claim 12
Dependent Claim
12 words
A method according to claim 9, wherein said tartrate is a diester.
Claim 13
Dependent Claim
23 words
A method according to claim 10, wherein the ester is a dialkyl ester of alkyl groups of from 1 to 6 carbon atoms.
Claim 14
Dependent Claim
12 words
A method according to claim 9, wherein said tartrate is an amide.
References Cited (Backward Citations)
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| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1987-09-11 | 1988-03-12 | 1988-09-11 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1991-09-11 | 1992-03-12 | 1992-09-11 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1995-09-11 | 1996-03-12 | 1996-09-11 | $7700.00 | Window Closed / Lapsed |