Catalytic osmium-assisted oxidative cleavage of olefins

Details Catalytic osmium-assisted oxidative cleavage of olefins Catalytic osmium-assisted oxidative cleavage of olefins

2003-01-13

2004-09-07

Richter, Johann (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Oxygen containing

C568S317000, C568S356000, C568S398000, C568S430000, C568S435000, C568S485000, C562S512200, C562S521000, C562S531000, C562S535000, C560S114000, C560S115000, C560S207000, C560S210000

Reexamination Certificate

active

06787671

ABSTRACT:

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
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Reference to a “Computer Listing Appendix submitted on a Compact Disc”
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BACKGROUND OF THE INVENTION
(1) Field of the Invention
The present invention relates to an osmium-assisted process for the oxidative cleavage of oxidizable organic compounds such as unsaturated organic compounds, including alkenes and olefins into aldehydes, carboxylic acids, esters, or ketones. The process uses a metal catalyst comprising osmium and a peroxy compound selected from the group consisting of peroxymonosulfuric acid and salts thereof to oxidatively cleave the oxidizable organic compound. In particular, the process enables aldehydes, carboxylic acids, esters, or ketones to be selectively produced from the corresponding mono-, 1,1-di-, 1,2-di-, tri-, or tetra-substituted olefins in a reaction that produces the result of ozonolysis but with fewer problems. The present invention further provides a process for oxidizing an aldehyde alone or with the osmium in an interactive solvent to produce an ester or carboxylic acid.
(2) Description of Related Art
In organic synthesis, oxidations and reductions are the key reactions for organic chemists. In particular, oxidative processes are essential components to the success of organic synthesis. Such processes include (1) metal assisted oxidative cleavage of alkenes (potassium permanganate) (Arney et al,. J. Org. Chem. 58: 6126
—
6128 (1993); Lee et al., J. Org. Chem. 44: 2726
—
2730 (1979)), (2) oxidative cleavage of diols (sodium periodate) (Gupta et al., J. Chem. Soc._Perkin Trans. 1: 2970
—
2973 (1981); Schmid et al., J. Org. Chem. 56: 4056
—
4058 (1991); Price et al., J. Am. Chem. Soc. 64: 552
—
554 (1942)), and (3) ozonolysis (Hon et al., Tetrahedron Lett. 34: 6591
—
6594 (1993); Schreiber et al., Tetrahedron Lett. 23: 3867
—
3870 (1982); Schreiber et al., J. Am. Chem. Soc. 110: 6210
—
6218 (1988)).
While numerous oxidative and reductive processes have been reported in the prior art, when it comes to cleaving or oxidizing carbon—carbon double bonds in oxidizable organic compounds to form aldehydes, ketones, carboxylic acids, or esters, there are two primary processes for cleaving the organic compounds, either (i) transform the organic compound into a 1,2-diol followed by cleavage with NaIO
4
or similar oxidant, or (ii) ozonolysis which transforms the organic compound into a variety of symmetrically or desymmetrically functionalized products depending on the workup conditions.
There are processes for oxidatively cleaving olefins such as oxidative cleavage of diols and ozonolysis, however, while these processes have specific advantages, they also have serious drawbacks. For example, potassium permanganate (KMnO4) is a cheap and useful oxidant, but it is not soluble in many organic solvents and it is often non_specific, which means that undesired oxidations occur during the oxidation which makes the workup tedious (Viski et al., J. Org. Chem. 51: 3213
—
3214 (1986)). In particular, permanganate is not a selective oxidant; thus, there are many possible side reactions in processes that use KMnO4 (Lee et al., J. Am. Chem. Soc. 105: 3188
—
3191 (1983)). Therefore, much of the work in the area of oxidative cleavage of alkenes using permanganate has been focused on the use of various phase transfer catalysts and solid supported reagents (Harris et al., Tetrahedron Lett. 38: 981
—
984 (1997); Ferreira et al., J. Org. Chem. 52: 3698
—
3699 (1987); Clark et al., J. Chem. Soc._Chem. Commun., 635
—
636 (1982); Noureldin et al., Tetrahedron Lett. 22: 4889
—
4890 (1981); Lee et al., J. Org. Chem. 58: 2918
—
2919 (1993)) to modify the reactivity and selectivity of the permanganate, but while these reactions are milder and more selective than permanganate itself, this has not proved to be a general solution to the problem.
Sodium periodate (NaIO
4
) is another useful reagent for cleaving diols. This reagent is also limited by its insolubility in organic solvents (Schmid et al., J. Org. Chem. 56: 4056
—
4058 (1991)). To increase the solubility and reactivity of the oxidant, processes have been developed that use quaternary alkyl ammonium periodate (Santaniello et al., Tetrahedron Lett. 21: 2655
—
2656 (1980); Keck et al., Tetrahedron Lett. 78: 4763
—
4766 (1978)), potassium metaperiodate along with phase transfer catalysts (Kalsi et al., Chem. Ind., 394
—
395 (1987)), and silica gel supported NaIO
4
(Daumas et al., Synthesis, 64
—
65 (1989)). While these modifications have to some extent been successful, the primary drawback of these modified reactions is that it is necessary to convert the carbon double bond to a diol before it can be cleaved. As an alternative, catalytic osmium tetroxide (OsO
4
) and NaIO
4
have been used together to oxidatively cleave olefins in a one pot process (Cainelli et al., Synthesis, 47
—
48 (1989)). However, this reaction often produces undesirable byproducts. To reduce the production of undesirable byproducts, the diol precursor is prepared in a separate reaction which is then used in a second periodate cleavage reaction to produce the cleavage product. Therefore, the process is still a two step process instead of the more desirable one pot process. Furthermore, other 1,2_diols within target molecules needs to be protected from oxidative cleavage.
The over-oxidation pathway, providing &agr;-hydroxy ketones, aldehydes, and carboxylic acids, is seldom described in literature for osmium tetroxide without the use of NaIO
4
. OsO
4
is much better known for formation of 1,2-diols (Shroder, Chem. Rev. 80: 187-213 (1980); Gobel et al., Angew. Chem.-Intl. Ed. Engl. 32: 1329-1331 (1993); Ogino et al., Tetrahedron Lett. 32: 3965-3968 (1991)) by hydrolysis of an intermediate osmate ester. Classically, conditions that usually promote higher levels of over-oxidation include catalytic OsO
4
with hydrogen peroxide (Milas et al., J. Am. Chem. Soc. 81: 4730-4733 (1959)) or tert-butyl hydrogen peroxide (Sharpless et al., J. Am. Chem. Soc. 22: 1287-1290 (1976)) as co-oxidants.
U.S. Pat. No. 3,946,065 to Matsui et al. discloses that a combination agent such as osmium tetroxide-sodium periodate or potassium permanganate-sodium periodate can be used to oxidize bicycloheptene to bicyclopentane. Also disclosed is a two-step process for cleaving the double bond of bicycloheptene by oxidizing the double bond to a vicinal alcohol using osmium tetroxide or peracid and then oxidizing the resulting single carbon bond with periodic acid or its metal salts, lead tetraacetate, a manganese compound, or a chromium compound.
In the prior art, the standard process for oxidative cleavage of olefins is ozonolysis. This reaction has been well_developed and yields aldehydes or carboxylic acids upon reductive or oxidative workup, respectively (Schreiber et al., Tetrahedron Lett. 23: 3867
—
3870 (1982)). Desymmetrization of the carbonyl functionality upon cleavage of cyclic olefins is also possible through the use of interactive solvents that yield an ester and an aldehyde (Hon et al., Tetrahedron Lett. 34: 6591
—
6594 (1993); Schreiber et al., J. Am. Chem. Soc.110: 6210
—
6218 (1988)).
Ozonolysis is a unique reaction that enables the cleavage of double-bonded carbons with ozone to yield aldehydes, carboxylic acids, or esters, which are then used as starting materials for producing a variety of important organic compounds. Ozonolysis is used by the petroleum industry to process crude oil into many small pure organic molecules, which are then used to make a variety of petrochemical products. While ozonolysis of crude oil is the primary commercial process for producing these important organic compounds, many of the ozonolysis reactions are low yielding. Furthermore, ozonolysis is an inherently dangerous process. The ozonides produced during ozonolysis are particularly dangerous and pose the risk of explosion. Therefore, an alternative reaction that is able to perform in a manner similar to ozonolysis would be highly desirable.
As important as ozonolysis has proved to be in synthetic che

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