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US 9,284,270 B2Granted
Boronic acid catalysts and methods of use thereof for activation and transformation of carboxylic acids
AssigneesThe Governers of the University of Alberta, GreenCentre Canada
InventorsDennis Hall, Nicolas Gernigon, Raed M. Al-Zoubi, Paul D. Thornton
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Abstract
The present application provides methods and catalysts for activation of carboxylic acids for organic reactions. In particular, methods are disclosed for direct nucleophilic addition reactions, such as, amidation reactions with amines, cycloadditions, and conjugate additions, using boronic acid catalysts of formula I, II or III: Also included are novel boronic acid catalysts of formula IV, V and III:
Claims21
A method for electrophilic activation of a carboxylic acid comprising combining a carboxylic acid-containing compound and a boronic acid compound of formula I, II or III:
- wherein
- R1 is a lone pair-containing heteroatom substituent;
- A is a 5 or 6-membered heteroaromatic ring comprising at least one heteromoiety selected from O, S, NH or NC1-4alkyl in which the R1 and B(OH)2 groups are ortho to each other, and which is optionally substituted with one or more additional substituents independently halo, R2a, OR2a, NR2aR2b, SR2a, S(O)R2a, SO2R2a, SeR2a or PR2aR2bR2c;
- R2a, R2b and R2c are independently C1-4alkyl or C6-10aryl;
- at least one of R3 and R5 is a lone pair-containing, heteroatom substituent and the other of R3 and R5 is independently H, halo, R6a, C1-4alkyleneR6a, OR6a, NR6aR6b, SR6a, S(O)R6a, SO2R6a, SeR6a or PR6aR6bR6c;
- R4 is H, halo, R6a, C1-6alkyleneR6a, OR6a, NR6aR6b, SR6a, S(O)R6a, SO2R6a, SeR6a or PR6aR6bR6c;
- R6a, R6b and R6c are independently C1-20alkyl or C6-14aryl;
- R7 is halo;
- R8 is OC1-6alkyl, OC6-10aryl or OC1-4alkyleneC6-10aryl;
- and
- each alkyl, aryl and alkylene group is unsubstituted or substituted by one or more halo, OC1-4alkyl, OC1-4alkyleneC6-10aryl and/or OC6-10aryl,
- under conditions for the electrophilic activation of the carboxylic acid.
9 more elements
A compound of:
- formula III:
- wherein
- R7 is I;
- and
- R8 is OC1-6alkyl, OC6-10aryl or OC1-4alkyleneC6-10aryl, with the proviso that R8 is not OMe or OBn;
- or
- formula IV:
- wherein
- R9 is I;
- R11 is H, halo, R12a, C1-4alkyleneR12a, OR12a, NR12aR12b, SR12a, S(O)R12a, SO2R12a, SeR12a or PR12aR12bR12c;
- R10 is H, halo, R12a, C1-4alkyleneR12a, OR12a, NR12aR12b, SR12a, S(O) R12a, SO2R12a, SeR12a or PR12aR12bR12c;
- R12a, R12b and R12c are independently C1-4alkyl or C6-10aryl;
- and
- each alkyl, aryl and alkylene is unsubstituted or substituted by one or more halo, OC1-4alkyl, OC1-4alkyleneC6-10aryl and/or OC6-10aryl;
- or
- formula V:
- wherein:
- R13 is I;
- R14 and R15 are independently H, halo, R16a, C1-6alkyleneR16a, OR16a, NR16aR16b, SR16a, S(O)R16a, SO2R16a, SeR16a or SiR16aR16bR16c;
- R16a, R16b and R16c are independently C1-20alkyl or C6-14aryl;
- and
- each alkyl, aryl and alkylene group is unsubstituted or substituted by one or more halo, OC1-4alkyl, OC1-4alkyleneC6-10aryl and/or OC6-10aryl.
19 more elements
A catalyst system comprising a boronic acid compound of formula I, II or III:
- wherein
- R1 is a lone pair-containing heteroatom substituent;
- A is a 5 or 6-membered heteroaromatic ring comprising at least one heteromoiety selected from O, S, NH or NC1-4alkyl in which the R1 and B(OH)2 groups are ortho to each other, and which is optionally substituted with one or more additional substituents independently halo, R2a, OR2a, NR2aR2b, SR2a, S(O)R2a, SO2R2a, SeR2a or PR2aR2bR2c;
- R2a, R2b and R2c are independently C1-4alkyl or C6-10aryl;
- at least one of R3 and R5 is a lone pair-containing, heteroatom substituent and the other of R3 and R5 is independently H, halo, R6a, C1-4alkyleneR6a, OR6a, NR6aR6b, SR6a, S(O)R6a, SO2R6a, SeR6a or PR6aR6bR6c;
- R4 is H, halo, R6a, C1-6alkyleneR6a, OR6a, NR6aR6b, SR6a, S(O)R6a, SO2R6a, SeR6a or PR6aR6bR6c;
- R6a, R6b and R6c are independently C1-20alkyl or C6-14aryl;
- R7 is halo;
- R8 is OC1-6alkyl, OC6-10aryl or OC1-4alkyleneC6-10aryl;
- and
- each alkyl, aryl and alkylene group is unsubstituted or substituted by one or more halo, OC1-4alkyl, OC1-4alkyleneC6-10aryl and/or OC6-10aryl,
- wherein:
- the boronic acid compound is bound to or adsorbed on a solid support;
- or
- the catalyst system further comprises a means for adsorbing water.
12 more elements
A composition comprising:
- (a) a boronic acid compound of formula I, II or III:
- wherein
- R1 is a lone pair-containing heteroatom substituent;
- A is a 5 or 6-membered heteroaromatic ring comprising at least one heteromoiety selected from O, S, NH or NC1-4alkyl in which the R1 and B(OH)2 groups are ortho to each other, and which is optionally substituted with one or more additional substituents independently halo, R2a, C1-44alkyleneR2a, OR2a, NR2aR2b, SR2a, S(O)R2a, SO2R2a, SeR2a or PR2aR2bR2c;
- R2a, R2b and R2c are independently C1-4alkyl or C6-10aryl;
- at least one of R3 and R5 is a lone pair-containing, heteroatom substituent and the other of R3 and R5 is independently H, halo, R6a, C1-4alkyleneR6a, OR6a, NR6aR6b, SR6a, S(O)R6a, SO2R6a, SeR6a or PR6aR6bR6c;
- R4 is H, halo, R6a, C1-6alkyleneR6a, OR6a, NR6aR6b, SR6a, S(O)R6a, SO2R6a, SeR6a or PR6aR6bR6c;
- R6a, R6b and R6c are independently C1-20alkyl or C6-14aryl;
- R7 is halo;
- R8 is OC5-6alkyl or OC1-4alkyleneC6-10aryl;
- and
- each alkyl, aryl and alylene group is unsubstituted or substituted by one or more halo, OC1-4alkyl, OC1-4alkyleneC6-10aryl and/or OC6-10aryl;
- (b) a carboxylic acid-containing compound;
- and
- (c) a solvent, wherein the boronic acid compound is present at an amount of about 25 mol% or less, based on the amount of carboxylic acid-containing compound.
12 more elements
Dependencies are inferred from the claim text.