Method for preparing allylic alcohols
AssigneeIowa State University Research Foundation, Inc.
InventorRichard C. Larock
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Abstract
The present invention provides a method for preparing allylic alcohols by the palladium-catalyzed cross-coupling of vinylic epoxides and aryl halides, vinylic halides or vinylic triflates.
Claims20
A method for preparing allylic alcohols comprising reacting (a) ArI or ArBr, wherein Ar is substituted aryl or unsubstituted aryl or (b) a compound of the formula (R.sup.1)(R.sup.2)C.dbd.C(R.sup.3)X, wherein X is I or Br, or trifluoromethanesulfonyloxy, and R.sup.1 R.sup.2 and R.sup.3 are H, (C.sub.1 -C.sub.8 ) alkyl, Ar, Ar (C.sub.1 -C.sub.4 ) alkyl or R.sup.1 and R.sup.3 taken together are --(CH.sub.2).sub.q -, wherein q is at least 3;
- with a vinylic epoxide of the formula (I):
- ##STR44## wherein R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are individually H, Ar or (C.sub.1 -C.sub.8)alkyl, in the presence of effective amounts of a Pd catalyst, an organic base, a formate and a chloride ion source, in an organic solvent, to yield an allylic alcohol of the general formula (II):
- Y-CH.sub.2 -C(R.sup.4).dbd.C(R.sup.5)C(R.sup.6)(R.sup.7)OH (II)
- wherein Y is Ar or (R.sup.1)(R.sup.2)C.dbd.C(R.sup.3)-, wherein Ar, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are as defined above
A method for preparing allylic alcohols comprising reacting (a) ArI or ArBr, or (b) a compound of the formula (R.sup.1)(R.sup.2)C.dbd.C(R.sup.3)X, wherein X is I, Br, or trifluoromethanesulfonyloxy, and R.sup.1, R.sup.2 and R.sup.3 are H, (C.sub.1 -C.sub.8)alkyl, Ar, Ar(C.sub.1 -C.sub.4) alkyl or R.sup.1 and R.sup.3 taken together are --(CH.sub.2).sub.q -, wherein q is at least 3;
- with a vinylic epoxide of the formula (I):
- ##STR45## wherein R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are individually H, Ar or (C.sub.1 -C.sub.8) alkyl, in the presence of effective amounts of a Pd(0) or Pd(II) catalyst, an organic base that is soluble in the reaction media, a formate of the formula M+O.sub.2 CH--, wherein M is an alkali metal or ammonium salt, and a chloride ion source chosen from a group consisting of tetra(C.sub.1 -C.sub.22)alkyl- or tetraaryl ammonium chlorides, tetra(C.sub.1 -C.sub.20)alkyl or tetraaryl phosphonium chlorides and alkali metal chlorides, in an organic solvent, to yield an allylic alcohol of the general formula (II):
- Y-CH.sub.2 -C(R.sup.4).dbd.C(R.sup.5)C(R.sup.6)(R.sup.7)OH (II)
- wherein Y is Ar or (R.sup.1 (R.sup.2)C.dbd.C(R.sup.3)-, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, and R.sup.7 are as defined above and Ar is a substituted or unsubstituted (C.sub.6 -C.sub.10) aryl.
A method for preparing allylic alcohols comprising reacting (a) ArI or ArBr, or (b) a compound of the formula (R.sup.1)(R.sup.2)C.dbd.C(R.sup.3)X, wherein X is 1, Br, or trifluoromethanesulfonyloxy, and R.sup.1, R.sup.2 and R.sup.3 are H, (C.sub.1 -C.sub.8)alkyl, Ar, Ar(C.sub.1 -C.sub.4)alkyl or R.sup.1 and R.sup.3 taken together are --(CH.sub.2).sub.q --, wherein q is at least 3;
- with a vinylic epoxide of the formula (I):
- ##STR46## wherein R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are individually H, Ar or (C.sub.1 -C.sub.8)alkyl, in the presence of effective amounts of a Pd(0) or Pd(II) catalyst, an organic base chosen from a group consisting of a trialkyl amine or a dicycloalkyl-(alkyl)amine of about 6-20 carbon atoms, a formate of the formula M+O.sub.2 CH--, wherein M is chosen from a group consisting of Li+, Na+, K+ or ammonium, and a chloride ion source chosen from a group consisting of a tetra(C.sub.1 -C.sub.22)alkyl- or a tetraaryl ammonium chloride, tetra(C.sub.1 -C.sub.20)alkyl or tetraaryl phosphonium chloride and alkali metal chloride, in an organic solvent, to yield an allylic alcohol of the general formula (II):
- Y-CH.sub.2 -C(R.sup.4).dbd.C(R.sup.5)C(R.sup.6)(R.sup.7)OH (II)
- wherein Y is Ar or (R.sup.1 (R.sup.2)C.dbd.C(R.sup.3)-, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, and R.sup.7 are as defined above and wherein Ar is a substituted or unsubstituted (C.sub.6 -C.sub.10)aryl and the substituents are chosen from the group consisting of Ar, Br, C.sub.1, F, formyl, amino, nitro, --CH(OCH.sub.3).sub.2, --CH(OEt).sub.2, --CO.sub.2 R, --CN, (C.sub.1 -C.sub.4)alkyl, (C.sub.1 -C.sub.4)alkoxy, ArO-, 3,4-methylene-dioxy, (C.sub.1 -C.sub.4)alkoxycarbonyl, hydroxy(C.sub.1 -C.sub.4)alkyl, (R)(R)N and (R)S-, wherein each R is (C.sub.1 -C.sub.4) alkyl or phenyl.
Dependencies are inferred from the claim text.