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CAPLUS COPYRIGHT 2007 ACS on STN
| TITLE:
| Copper-catalyzed formation of carbon-heteroatom and carbon-carbon bonds by arylation and vinylation of amines, amides, hydrazides, heterocycles, alcohols, enolates, and malonates, using aryl, heteroaryl, and vinyl halides and analogs |
| INVENTOR(S):
| Buchwald, Stephen L.; Klapars, Artis; Antilla, Jon C.; Job, Gabriel E.; Wolter, Martina; Kwong, Fuk Y.; Nordmann, Gero; Hennessy, Edward J. |
| PATENT ASSIGNEE(S):
| Massachusetts Institute of Technology, USA |
| SOURCE:
| PCT Int. Appl., 306 pp. CODEN: PIXXD2 |
| LANGUAGE:
| English |
PATENT INFORMATION: PATENT NO. KIND DATE APPLICATION NO. DATE
--------------- ---- -------- -------------------- --------
WO 2002085838 A1 20021031 WO 2002-US12785 20020424
W: AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, BZ, CA, CH, CN,
CO, CR, CU, CZ, DE, DK, DM, DZ, EC, EE, ES, FI, GB, GD, GE, GH,
GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR,
LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, MZ, NO, NZ, OM, PH,
PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TN, TR, TT, TZ,
UA, UG, UZ, VN, YU, ZA, ZM, ZW
RW: GH, GM, KE, LS, MW, MZ, SD, SL, SZ, TZ, UG, ZM, ZW, AT, BE, CH,
CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE, TR,
BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, ML, MR, NE, SN, TD, TG
CA 2445159 A1 20021031 CA 2002-2445159 20020424
AU 2002258946 A1 20021105 AU 2002-258946 20020424
US 2003065187 A1 20030403 US 2002-128981 20020424
US 6759554 B2 20040706
EP 1390340 A1 20040225 EP 2002-728925 20020424
R: AT, BE, CH, DE, DK, ES, FR, GB, GR, IT, LI, LU, NL, SE, MC, PT,
IE, SI, LT, LV, FI, RO, MK, CY, AL, TR
CN 1518534 A 20040804 CN 2002-812587 20020424
JP 2004536798 T 20041209 JP 2002-583366 20020424
CN 1854128 A 20061101 CN 2006-10082481 20020424
US 2004019216 A1 20040129 US 2003-435719 20030508
US 6867298 B2 20050315
US 2005215794 A1 20050929 US 2005-28500 20050104
US 7115784 B2 20061003
US 2006264673 A1 20061123 US 2006-431154 20060509
ABSTRACT:
The invention relates to copper-catalyzed carbon-heteroatom and carbon-carbon bond-forming methods. More specifically, it relates to the arylation, heteroarylation, and vinylation of compds. with nucleophilic N, O, and C atoms, by aryl and vinyl halides and sulfonates, using various Cu-based catalysts and suitable ligands. The methods provide an inexpensive alternative to corresponding palladium-catalyzed reactions. Thus, the invention includes copper-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of an amide or amine moiety and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. The invention provides similar copper-catalyzed reactions of acyl hydrazines (i.e., hydrazides). The invention further relates to copper-catalyzed arylation and vinylation of nitrogen-contg. heteroaroms., e.g., indole, pyrazole, and indazole, at nitrogen. Similarly, the invention provides copper-catalyzed arylation and vinylation of alcs. at the oxygen atom. Finally, the invention provides copper-catalyzed methods of forming a carbon-carbon bond between reactants with nucleophilic carbon atoms, e.g., an enolate or malonate anion, and the activated carbon of the aryl, heteroaryl, or vinyl halides or sulfonates. Importantly, all of the invention methods are relatively inexpensive to practice due to the low cost of the copper catalysts. For example, a claimed method for amines, amides, and hydrazides involves reaction of halides and sulfonates Z-X [Z = (un)substituted aryl, heteroaryl, or alkenyl; X = iodo, Br, Cl, alkylsulfonate, arylsulfonate] with amines and derivs. R-NH-R' [R = alkyl, cycloalkyl aralkyl, aryl, heteroaryl, formyl, acyl, alkoxycarbonyl, aryloxycarbonyl, acylamino, etc.; R' = H, alkyl, cycloalkyl, (hetero)aralkyl, (hetero)aryl, formyl, acyl, amino, or amidino; with provisos] in the presence of a copper atom or ion and a ligand in the presence of a Bronsted base, yielding a corresponding arylated or vinylated product Z-NRR'. Thus, arylation of benzamide with allyl 4-iodobenzoate in dioxane solvent in the presence of CuI (catalyst), trans-1,2-cyclohexanediamine (ligand), and K3PO4 (base), at 110.degree. in a resealable Schlenk tube, gave the expected product I in 91% yield. Similarly, 2-pyrrolidinone was N-heteroarylated by 2-iodothiophene under the same conditions to give II in quant. yield. Indole was N-arylated by 4-bromotoluene to give III in 95% yield. A similar reaction of (E)-2-undecen-1-ol with (E)-1-iodo-1-decene using CuI, 3,4,7,8-tetramethyl-1,10-phenanthroline, and Cs2CO3 in PhMe at 80.degree., gave 68% (E,E)-1-(dec-1-enyloxy)undec-2-ene.
Updated 8/24/2007 12:46:32 PM
