Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing
Patent
1993-10-06
1997-04-01
Nazario-Gonzalez, Porfirio
Organic compounds -- part of the class 532-570 series
Organic compounds
Heavy metal containing
540541, 544 4, 544 64, 544225, 546 2, 548101, 548402, 549 3, 549206, 549531, 549533, 556 45, C07F 1300, C07D30112, C07D30106
Patent
active
056167504
DESCRIPTION:
BRIEF SUMMARY
This application was filed under 35 U.S.S. .sctn.371 as a request for U.S. examination of International application No. PCT/GB93/01666, filed on Aug. 5, 1993.
This invention relates to novel catalysts and their use in the conversion of certain olefins into chirally enriched epoxides.
WO/91/14694 describes certain catalysts of the following formula (A): ##STR2## in which
M is a transition metal ion, A is an anion, and n is either 0, 1 or 2. At least one of X.sub.1 or X.sub.2 is selected from the group consisting or silyls, aryls, secondary alkyls and tertiary alkyls; and at least one of X.sub.3 or X.sub.4 is selected from the same group. Y.sub.1, Y.sub.2, Y.sub.3, Y.sub.4, Y.sub.5 and Y.sub.6 are independently selected from the group consisting of hydrogen, halides, alkyls, aryl groups, silyl groups, and alkyl groups bearing heteroatoms such as alkoxy and halide. Also, at least one of R.sub.1, R.sub.2, R.sub.3 and R.sub.4 is selected from a first group consisting of H, CH.sub.3, C.sub.2 H.sub.5 and primary alkyls. Furthermore, if R.sub.1 is selected from said first group, then R.sub.2 and R.sub.3 arc selected from a second group consisting of alkyl groups, heteroatom-bearing aromatic groups, secondary alkyls and tertiary alkyls. If R.sub.2 is selected from said first group, then R.sub.1 and R.sub.4 are selected from said second group. If R.sub.3 is selected from said first group, then R.sub.1 and R.sub.4 are selected from said second group. If R.sub.4 is selected from said first group, then R.sub.2 and R.sub.3 are selected from said second group.
Such catalysts are described as being useful in enantioselectively epoxidising a prochiral olefin.
Structurally distinct catalysts have now been prepared which surprisingly possess the ability to catalyse the enantioselective expoxidation of certain prochiral olefins.
Accordingly, the present invention provides a compound of formula (I): ##STR3## in which M is a transition metal ion; A is a counter-ion if required; 3; where R' is hydrogen or an organic group; alkyl, hydrogen, alkylcarbonyl, or arylcarbonyl or SO.sub.n where n is 0 or an integer 1 or 2, with the proviso that B and E are not simultaneously CH.sub.2 and that when B is oxygen, NR.sup.d or SO.sub.n, then r cannot be 0, and when E is oxygen, NR.sup.d or SO.sub.n, then t cannot be 0; R.sub.9 and R.sub.10 are independently hydrogen, alkyl or alkoxy.
Suitable transition metal ions, M, include Mn, Cr, Fe, Ni, Co, Ti, V, Ru and Os in an appropriate oxidation state.
Preferably the transition metal ion, M, is Mn in oxidation state (II) or (III).
It should be appreciated that in some cases for example when M is Mn (II), a counter-ion is not required.
Suitable counter-ions, A, include those anions mentioned in WO 91/14694.
Preferably, A is chloride.
Suitable organic groups R' include alkyl, alkylcarbonyl, arylcarbonyl or aryl derivatives.
Particular examples of R' include substituted alkyl groups.
One example of R' is triphenylmethyl.
Preferably s and t are zero, r is 1 and R.sup.a is hydrogen, B is oxygen and E is CH.sub.2 ; or r, s and t are 1, R.sup.a, R.sup.b and R.sup.c are hydrogen and B and E are both oxygen; or s is zero, r and t are both 1, R.sup.a is hydrogen or triphenylmethyloxymethylene and R.sup.c is hydrogen, B is oxygen and E is --CH.sub.2 --; or r and t are both 1, s is zero, R.sup.a and R.sup.c are hydrogen, B is NR.sup.d where R.sup.d is phenyl carbonyl and E is CH.sub.2.
Suitably, R.sub.2, R.sub.4, R.sub.5 and R.sub.7 each independently represent hydrogen.
Suitably R.sub.1, R.sub.3, R.sub.6 and R.sub.8 each independently represent C 1-6 alkyl.
Favourably R.sub.1 and R.sub.8 represent branched alkyl groups such as tertiary alkyl groups.
R.sub.3 and R.sub.6 also advantageously represent branched alkyl groups.
One preferred example for each of R.sub.1 and R.sub.8 is tertiary butyl.
Particular examples of R.sub.3 and R.sub.6 are tertiary butyl and methyl.
Examples of R.sub.2, R.sub.4, R.sub.5 and R.sub.7 are hydrogen.
The term `alkyl` when used alone or when forming pan of other groups (for exampl
REFERENCES:
patent: 5250285 (1993-10-01), Lauffer et al.
patent: 5420314 (1995-05-01), Katsuki et al.
Journal of American Chemical Society, W. Zang, `Enantioselective Epoxydation of Unfunctionalized Olefins Catalyzed By (Salen) Manganee Complex`, vol. 112, Mar. 12, 1990, pp. 2801-2803.
Journal of American Chemical Society, K. Srinivasan, `Epoxidation of Olefins With Cationic (Salen)MN Complexes.` vol. 108, 1986, pp. 2309-2320.
Attrill Robin P.
Bell David
Miller David
Kanagy James M.
Lentz Edward T.
Nazario-Gonzalez Porfirio
SmithKline Beecham Plc
Venetianer Stephen
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