Second cycle asymmetric dihydroxylation reaction
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IPC분류정보
국가/구분 |
United States(US) Patent
등록
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국제특허분류(IPC7판) |
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출원번호 |
US-0941410
(2001-08-28)
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발명자
/ 주소 |
- Sharpless, K. Barry
- Andersson, Malin
- Epple, Robert
- Fokin, Valery
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출원인 / 주소 |
- The Scripps Research Institute
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인용정보 |
피인용 횟수 :
0 인용 특허 :
4 |
초록
A process for catalyzing asymmetric dihydroxylations of olefins employs an Os(VI) complex as a catalytic intermediate in the formation of chiral vicinal diol products. The process requires a chiral bidentate ligand that favors diol formation in the “second cycle” of asymmetric dihydroxylation.
대표청구항
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1. A process for catalyzing a second-cycle asymmetric dihydroxylation reaction for converting an olefin substrate to a chiral vicinal diol product, said process comprising the following steps:Step A: mixing the olefin substrate with a catalytic amount of a chiral bidentate ligand in an aqueous solve
1. A process for catalyzing a second-cycle asymmetric dihydroxylation reaction for converting an olefin substrate to a chiral vicinal diol product, said process comprising the following steps:Step A: mixing the olefin substrate with a catalytic amount of a chiral bidentate ligand in an aqueous solvent, the aqueous solvent optionally being an alcohol/water solvent mixture, the chiral bidentate ligand being represented by the following structure: wherein:R is a radical selected from the group consisting of hydrogen, carboxylic acid, phenyl, 1-naphthyl, 2-naphthyl, alkyl(C1-C12), cyclo-alkyl(C3-C12), carbamoyl, N-alkyl(C1-C12) carbamoyl, and N,N-alkyl(C1-C12) carbamoyl, wherein the phenyl, 1-naphthyl, and 2-naphthyl radicals ay optionally have substituents in any available position; R1 is a radical selected from the group consisting of carboxylic acid, carbamoyl, N-alkyl(C1-C12) carbamoyl, and N,N-dialkyl(C1-C12) carbamoyl; R2 is a radical selected from the group consisting of hydrogen , alkyl(C1-C12), aryl, and heteroaryl; and X and Y are radicals independently selected from the group consisting of hydroxyl, amino, N-alkyl(C1-C12)sulfonylamino, N-arylsulfonylamino, and N-heteroarylsulfonylamino; with the following provisos: if X is not a hydroxyl group, then Y must be a hydroxy group; if Y is not a hydroxyl group then X must be a hydroxyl group; and at least one of the following must be a carboxylic acid group: R, R1 or R2; and then Step B: adding to the mixture of said Step A a stoichiometric amount or a stoichimetric excess of N-methyl morpholine N-oxide with respect to the olefin substrate and a catalytic amount of osmium tetraoxide under reaction conditions for catalyzing the second-cycle asymmetric dihydroxylation reaction for converting the olefin substrate to the chiral vicinal diol product. 2. A process according to claim 1 where the chiral bidentate ligand is selected from the group represented by the following structures: 3. A process according to claim 1 wherein the chiral ligand is an α-hydroxy-β-N-sulfonylamino carboxylic acid.4. A process according to claim 1 wherein the chiral ligand is an α-N-sulfonylamino-β-hydroxy carboxylic acid.5. A process according to claim 1 wherein chiral bidentate ligand has a concentration between 1 mol % and 10 mol %, with respect to the olefin substrate.6. A process according to claim 5 wherein, in said Step A, the chiral bidentate ligand has a concentration of 5 mol %, with respect to the olefin substrate.7. A process according to claim 6 wherein, in said Step B, the osmium tetraoxide has a concentration of between 0.1 mol % and 1 mol %, with respect to the olefin substrate.8. A process according to claim 7 wherein, in said Step B, the osmium tetraoxide has a concentration of approximately 0.2 mol %, with respect to the olefin substrate.9. A process according to claim 8, wherein the olefin substrate is an α,β-unsaturated carboxylic acid ester.10. A process according to claim 9 wherein the pH of the reaction mixture of said Step B is approximately 5.11. A process according to claim 10 wherein the alcohol used in the alcohol/water solvent mixture of said Step A is tertiary butyl alcohol.
이 특허에 인용된 특허 (4)
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Marko Istvan E. (Sheffield MA GB2) Sharpless K. Barry (Brookline MA), Ligand-accelerated catalytic asymmetric dihydroxylation.
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Sharpless K. Barry (LaJolla CA) Beller Matthias (Frankfurt am Main CA DEX) Blackburn Brent (San Francisco CA) Kawanami Yasuhiro (Kagawa MA JPX) Kwong Hoi-Lun (Somerville MA) Ogino Yasukazu (Tokyo JPX, Method for catalytic asymmetric dihydroxylation of olefins using heterocyclic chiral ligands.
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Kobayashi Shu,JPX, Osmium oxide composition.
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Boyapati Manoranjan Choudary IN; Naidu Sreenivasa Chowdari IN; Mannepalli Lakshmi Kantam IN; Kondapuram Vijaya Raghavan IN; Chinta Venkat Reddy Reddy IN, Preparation of new layered double hydroxides exchanged with osmate for asymmetric dihydroxylation of olefins to vicinal diols.
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