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US 6,762,329 B2Granted
Diaryl ether condensation reactions
AssigneeMassachusetts Institute of Technology
InventorsJean-Francois Marcoux, Sven Doye, Stephen Buchwald
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Abstract
One aspect of the present invention relates to novel reaction conditions that allow the efficient synthesis of diaryl ethers from arenes bearing a leaving group and arenols under relatively mild conditions. Another aspect of the present invention relates to the dramatic effects of acidic activators on Ullmann-type couplings involving electron-poor and/or relatively insoluble substrates.
Claims75
The method depicted in scheme 1:
- wherein
- Ar and Ar′ independently represent optionally substituted monocyclic or polycyclic aromatic or heteroaromatic moieties;
- X represents Cl, Br, I, —O3S(alkyl), or —O3S(aryl);
- Y represents O, S, Se, NR, PR, or AsR;
- Z represents H, a group that is lost under the reaction conditions to generate a negative charge on Y, or a group that is replaced by H under the reaction conditions;
- R represents H, alkyl, aryl, aralkyl, heteroalkyl, heteroaryl, trialkylsilyl, acyl, or sulfonyl;
- catalyst is selected from the group consisting of copper carboxylates, copper carbonates, copper sulfates, copper sulfonates, and copper halides;
- co-catalyst represents a uncharged molecule comprising a Lewis basic pair of electrons;
- alkali salt represents a salt selected from the group consisting of cesium bicarbonate, cesium carbonate, cesium, carboxylates, and cesium phosphates;
- the reaction takes place at a temperature in the range of about 25-150° C.;
- and
- the method is not conducted in an amine solvent or an aqueous solvent.
9 more elements
The method depicted in scheme 2:
- wherein
- Ar and Ar′ independently represent optionally substituted monocyclic or polycyclic aromatic or heteroaromatic moieties;
- X represents Cl, Br, I, —O3S(alkyl), or —O3S(aryl);
- Y represents O, S, Se, NR, PR, or AsR;
- Z represents H, a group that is lost under the reaction conditions to generate a negative charge on Y, or a group that is replaced by H under the reaction conditions;
- R represents H, alkyl, aryl, aralkyl, heteroalkyl, heteroaryl, trialkylsilyl, acyl, or sulfonyl;
- catalyst is selected from the group consisting of copper carboxylates, copper carbonates, copper sulfates, copper sulfonates, and copper halides;
- co-catalyst represents a uncharged molecule comprising a Lewis basic pair of electrons;
- acid activator is selected from the group consisting of carboxylic acids, amides, hydroxamic acids, phosphoric acids, phosphonic acids, phosphinic acids, sulfonic acids, sulfinic acids, sulfenic acids, alkylboronic acids, arylboronic acids, silicic acids, and thiols;
- alkali salt represents a salt selected from the group consisting of cesium bicarbonate, cesium carbonates, cesium carboxylates, and cesium phosphates;
- and
- the reaction takes place at a temperature in the range of about 25-150° C.
9 more elements
Dependencies are inferred from the claim text.