Patent DE-102009055183-B3 (DE)
Title: Preparing aryl-substituted nitroalkane derivatives comprises arylation of nitroalkene derivative with boroaryl compound in presence of palladium salt or palladium complex in water or in mixture of water and water miscible organic solvent
Inventor: EILITZ UWE DR
IPC: B01J31/16
Filed: 2009-12-22
Granted: 2011-12-08
Abstract: Preparing aryl-substituted nitroalkane derivatives (II) comprises arylation of nitroalkene derivatives (I) with boroaryl compounds in the presence of 0.1-10 mol.% of palladium salts or palladium complexes in water or in a mixture of water and water miscible organic solvent. Preparing aryl-substituted nitroalkane derivatives of formula (O 2N-CH 2-CH(Ar1)-X) (II) comprises arylation of nitroalkene derivatives of formula (O 2N-CH=CH-X) (I) with boroaryl compounds in the presence of 0.1-10 mol.% of palladium salts or palladium complexes in water or in a mixture of water and water miscible organic solvent. X : CR2OR1, CR(OR2) 2, C(=O)-Y1-R3 n, CN or CR4 3; R : H, optionally branched 1-12C-alkyl, 2-12C-alkenyl, 1-12C-alkynyl, 6-12C-aryl or 7-13C-alkylaryl; R1 : H, optionally branched 1-6C-alkyl, 3-6C-alkenyl, 3-6C-cycloalkyl, 6-10C-aryl, 7-11C-alkylaryl, tetrahydropyranyl, tetrahydrofuranyl, 4-methoxybenzyl, 3,4-dimethoxybenzyl, 2-nitrobenzyl, 4-nitrobenzyl, trimethylsilyl, triethylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, diphenylmethylsilyl, acetyl, pivaloyl, benzoyl, methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, 4-methoxybenzyloxycarbonyl, fluorenylmethyloxycarbonyl, trichloroethyloxycarbonyl or isobutyloxycarbonyl; either R2 : optionally branched 1-6C-alkyl, 3-6C-alkenyl, 3-6C-cycloalkyl, 6-10C-aryl, 7-11C-alkylaryl, 4-methoxybenzyl, 2-nitrobenzyl, 2,2,2-trichloroethyl, 2-bromoethyl or 2-trimethylsilylethyl; or R2+R2 : optionally saturated ring; Y1 : O (where n is 1) or N (where n is 2); either R3 : H, optionally branched 1-12C-alkyl, 6-10C-aryl or 7-11C-alkylaryl (optionally substituted by one or more halo, methoxy or nitro); or R3+R3 : optionally saturated ring that optionally additionally contains O or N atoms; R4 : H or halo, where at least one R4 is halo; Ar1 : aryl group comprising 6-14C-aryl or 3-14C-heteroaryl, having one or more heteroatom(s) comprising O, N or S, where the aryl group is optionally substituted with one or more halo, OR5, NR5R6, SR5, NO, NO 2, S(=O)-R5, SO 2R5, NSO 2N R5R6, SO 2NR5R6, COOR5, CHO, C(=O)R5, C(=O)NR5R6, Si(R5) 3, CN, OR7, NR5R8 or SR9, and the optionally branched 1-6C-alkyl, 2-6C-alkenyl, 6-10C-aryl, 3-10C-heteroaryl, 7-11C-alkylaryl, 4-11C-alkyl heteroaryl, 3-6C-cycloalkyl or 3-6C-cycloheteroalkyl groups are optionally together forms a optionally saturated ring, and optionally substituted by one or more halo, OR5, NR5R6, SR5, NO, NO 2, S(=O)-R5, SO 2-R5, NSO 2NR5R6, SO 2NR5R6, COOR5, CHO, C(=O)R5, C(=O)NR4R5, Si(R5) 3, CN, OR7, NR5R8 or SR9; R5, R6 : H, or 1-6C-alkyl, 2-6C-alkenyl, 6-10C-aryl, 3-10C-heteroaryl, 7-11C-alkylaryl, 4-11C-alkyl heteroaryl, 3-6C-cycloalkyl or 3-6C-cycloheteroalkyl, where the above groups are optionally together forms a optionally saturated ring; R7 : tetrahydropyranyl, tetrahydrofuranyl, 4-methoxybenzyl, 3,4-dimethoxybenzyl, 2-nitrobenzyl, 4-nitrobenzyl, trimethylsilyl, triethylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, diphenylmethylsilyl, acetyl, pivaloyl, benzoyl, methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, 4-methoxybenzyloxycarbonyl, fluorenylmethyloxycarbonyl, trichloroethyloxycarbonyl or isobutyloxycarbonyl; R8 : methoxycarbonyl, ethoxycarbonyl, tert-butyloxycarbonyl, allyloxycarbonyl, benzyloxycarbonyl, 4-methoxybenzyloxycarbonyl, fluorenylmethyloxycarbonyl, formyl, acetyl, benzoyl, 4-methoxybenzyl, benzenesulfonyl or 4-methylbenzenesulfonyl; R9 : tetrahydropyranyl, 4-methoxybenzyl, fluorenylmethyl, trimethylsilyl, triethylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, diphenylmethylsilyl, benzyloxycarbonyl or tert-butyloxycarbonyl; and n : 1 or 2. Independent claims are included for aryl substituted nitroalkane derivatives of formula (O 2N-CH 2-CH(Ar1)-C(=O)-N(R3) 2) (IV) (representative of (II)) and/or their enantiomers.