EP 1899358 A2 20080319 - NOVEL P-CHIRAL FUNCTIONALISED ARYLPHOSPHINES AND DERIVATIVES, THE PREPARATION AND USE THEREOF FOR ASYMMETRICAL CATALYSIS
Title (en)
NOVEL P-CHIRAL FUNCTIONALISED ARYLPHOSPHINES AND DERIVATIVES, THE PREPARATION AND USE THEREOF FOR ASYMMETRICAL CATALYSIS
Title (de)
NEUE P-CHIRALE FUNKTIONALISIERTE ARYLPHOSPHINE UND DERIVATE, IHRE HERSTELLUNG UND IHRE VERWENDUNG ZUR ASYMMETRISCHEN KATALYSE
Title (fr)
NOUVELLES ARYLPHOSPHINES P-CHIRALES ORTHO-FONCTIONNALISEES ET DERIVES: LEUR PREPARATION ET UTILISATION EN CATALYSE ASYMETRIQUE
Publication
Application
Priority
- FR 2006001394 W 20060620
- FR 0506226 A 20050620
Abstract (en)
[origin: FR2887253A1] Optically active organo phosphorus compound (I) in which the phosphorus atom carries chirality and a (hetero)aryl group functionalized in position ortho or 2, is new. Optically active organo phosphorus compound of formula (I) in which the phosphorus atom carries chirality and a (hetero)aryl group functionalized in position ortho or 2, is new. P 1>asymmetric P; m : >=1; n : 0-1; E : 2 electrons, BH 3, HBF 4, TfDH, HClO 4, HPF 6, HBr, HI, HCl, HF, CH 3COOH, CH 3COOH or MsOH; R 3>, R 4>H, 1-4C alkyl or 1-4C alkoxy (optionally substituted by F and/or 1-4C alkyl or 1-4C alkoxy (optionally substituted)); R 3>R 4>5-6C cycloalkane, dioxolane, dioxane or Ar e.g. naphth-1,8-diyl (optionally substituted); z : bond between (CR 3>R 4>) nand Z; Ar 1>4-14C (poly)aromatic ring (bonded to P 1>by a bond (x) and bonded to a group Z(CR 3>R 4>) nby a bond (y), where Z(CR 3>R 4>) nis in ortho or 2 position to P 1>) (optionally includes N, O, S or optionally carry N, O, Si, halo and/or optionally substituted 1-10C alkyl and/or alkoxy or form a cyclic ring of Ar and P as phosphino-Ar e.g. phosphinobenzene, 1-phosphinonaphtalene, 2-phosphinonaphtalene, N(R 5>)-2-methyl-7-phosphinoindole or N-(R 5>)-7-phosphinoindoline and Z(CR 3>R 4>) n-Ar-phosphino is N-(R 5>)-2-phosphinopyrrole or N(R 5>)-2-phosphmoindole); R 5>e.g. a carbon skeleton of formula (II); OR 5>(when m is 1) : e.g. 2,3- dihydro-2,2-dimethyl-7-benzofuranyl ring of formula (III); Z : OR 5>, SR 5>, SO 2R 5>, N(R 6>R 7>), C(O)N(R 6>R 7>), N(R 5>), 1-10C trialkylsilyl, triphenylsilyl, 5-14C (hetero)aryl (optionally substituted by F or 1-10C alkyl); A : C, O, S or TsN, CH, CH 2, Si(R 51>) 2-O-Si(R 51>) m1, benzene or pyridine; R 51>1-10C alkyl; m1 : >=1; A 1>-A 4>CH 2or (R 51>)CH; B 1>-B 4>CH 2, C(O), SO 2, (R 8>R 9>)Si, C(O)N or C(O)O; R 8>, R 9>1-18C alkyl, 5-8C cycloalkyl or 6-10C aryl (all substituted by alkyl, alkenyl or aryl, containing heteroatoms of O, N, Si, P or halo); k1-k4 : 0-10; l1-l4 : 0-1; x1-x4 : bonds between A and A 1>-A 4>; y1-y4 : bonds between A 1>-A 4>and B 1>-B 4>respectively; z1-z4 : bonds between B 1>-B 4>and O, S, N or NC(O) terminals; P 01>asymmetrical phosphorus atom with P 1>(where P 01>has absolute configuration); E 01>E; Q 1>C(Me) 2or Si(Me) 2; R 52>H, 1-10C alkyl e.g. methyl or tert-butyl; and either R 1>H, Cl, Br, I or F, 1-18C alkyl, 5-7C cycloalkyl, 4-14C (hetero)aryl (optionally substituted by alkyl, alkoxy or aryl and/or by heteroatoms e.g. O, N, Si, P, halo), 5-14C aryloxy, 1-18C alkoxy (optionally having C or substituted halo, nitrogenized groups of 4-6C aliphatic, 1-18C (di)alkylamino (where the alkyl have asymmetrical carbon atoms C and possibly substituted by heteroatoms) or Z(CR 3>R 4>) n-Ar); R 2>e.g. 1-18C alkyl, 5-7C cycloalkyl, 4-14C (hetero)aryl (optionally substituted by alkyl, alkoxy or aryl and/or by heteroatoms e.g. O, N, Si, P, halo), vinyl or alkoxy; or R 1>R 2>2-3C hydrocarbonated aminoalkoxy (containing asymmetrical carbon atoms C*). Full Definitions are given in the DEFINITIONS (Full Definitions) Field. Independent claims are included for: (1) the preparation of (I) using optically active oxazaphosphacycloalcane-borane of formula (Ib) derived from a optically active aminoalcohol of formula (HN(R 6>)-Q 2>-OH); (2) phosphine-metal complexes of formula M pL q(X 1>) r(S v) s(S 1>v) s1H tto carry out asymmetrical syntheses in organic chemistry, comprising a transition metal and at least optically active form of (I) as ligand; and (3) preparation of the phosphine-metal complexes comprising reacting the transition metal donor with (I) in the presence of a solvent. M : rhodium, ruthenium, iridium, cobalt, palladium, platinum, nickel or copper; L : optically active compound (I); S v, S 1>vH 2O, MeOH, EtOH, amine, 1,2-diamine (optionally chiral), pyridine, ketone e.g. acetone, ether e.g. THF, sulfoxide e.g. dimethyl sulfoxide, amide e.g. dimethyl formamide or N-methylpyrrolidinone, olefin e.g. ethylene, 1,3-butadiene, cyclohexadiene, 1,5-cyclo-octadiene, 2,5-norbornadiene, 1,3,5-cyclooctatriene, nitrile e.g. acetonitrile, benzonitrile, 5-12C arene or eta- aryl (optionally substituted by 1-5C alkyl, iso- or tert-alkyl, benzene, p-cymene, hexamethylbenzene or pentamethylcyclopentadienyl); p : 1-2; q : 1-4; r : 0-4; s, s1, t : 0-2; R 10>methyl, (trimethylsilyl)methyl, isopropyl, tert-butyl, adamantyl, 5-7C cycloalkyl, 4-14C aryl (optionally substituted) or ortho-Z(CR 03>R 04>) n-Ar; n : 0-1; Q 21>2-3C alkyl (having asymmetrical carbon, and bonded to N by R 06>containing a cycle); and Ar : phenyl or naphthyl (optionally substituted 1-10C alkyl and/or alkoxy (both optionally substituted or form a cycle)). Provided that when the complex cationic then X 1>is anionic ligand coordinant e.g. Cl, Br or I, anion groups e.g. OTf, BF 4, ClO 4, PF 06, SbF 6, BPh 4, B (C 6F 5) 4, B(3,5-di-CF 3-C 6H 3) 4, p-TsO, OAc or CF 3CO 2, pi -allyl, 2-methyl allyl. When the complex is anionic then X 1>is cation e.g. Li, Na, K or ammonium (optionally substituted by alkyl). [Image] [Image] [Image] [Image].
IPC 8 full level
C07F 9/50 (2006.01); B01J 27/14 (2006.01); C07F 5/02 (2006.01)
CPC (source: EP US)
B01J 31/2404 (2013.01 - EP US); B01J 31/2409 (2013.01 - EP US); B01J 31/2457 (2013.01 - EP US); C07B 53/00 (2013.01 - EP US); C07F 9/5022 (2013.01 - EP US); C07F 9/5027 (2013.01 - EP US); C07F 9/5045 (2013.01 - EP US); C07F 15/0046 (2013.01 - EP US); C07F 15/0053 (2013.01 - EP US); B01J 2231/32 (2013.01 - EP US); B01J 2231/321 (2013.01 - EP US); B01J 2231/323 (2013.01 - EP US); B01J 2231/52 (2013.01 - EP US); B01J 2231/643 (2013.01 - EP US); B01J 2231/645 (2013.01 - EP US); B01J 2531/001 (2013.01 - EP US); B01J 2531/16 (2013.01 - EP US); B01J 2531/821 (2013.01 - EP US); B01J 2531/822 (2013.01 - EP US); B01J 2531/824 (2013.01 - EP US); B01J 2531/827 (2013.01 - EP US); B01J 2531/828 (2013.01 - EP US); B01J 2531/845 (2013.01 - EP US); B01J 2531/847 (2013.01 - EP US)
Citation (search report)
See references of WO 2006136695A2
Designated contracting state (EPC)
AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR
DOCDB simple family (publication)
FR 2887253 A1 20061222; EP 1899358 A2 20080319; US 2010099875 A1 20100422; WO 2006136695 A2 20061228; WO 2006136695 A3 20070518
DOCDB simple family (application)
FR 0506226 A 20050620; EP 06778624 A 20060620; FR 2006001394 W 20060620; US 99340806 A 20060620