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CAS indexed 192 chemical substances from this document.
CAS subject entries for this document include: Phosphines; Boranes; Chirality; and 18 additional concepts. | |
CAPLUS COPYRIGHT 2007 ACS on STN
| TITLE:
| Preparation of new P-chiral ortho-functionalized arylphosphines their borane complexes and transition metal catalysts for asymmetric addition and substitution reactions |
| INVENTOR(S):
| Stephan, Michel Massoud; Mohar, Barbara |
| PATENT ASSIGNEE(S):
| Phosphoenix, Fr.; National Institute of Chemistry |
| SOURCE:
| Fr. Demande, 61pp. CODEN: FRXXBL |
| LANGUAGE:
| French |
PATENT INFORMATION: PATENT NO. KIND DATE APPLICATION NO. DATE
--------------- ---- -------- -------------------- --------
FR 2887253 A1 20061222 FR 2005-6226 20050620
WO 2006136695 A2 20061228 WO 2006-FR1394 20060620
W: AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BW, BY, BZ, CA, CH,
CN, CO, CR, CU, CZ, DE, DK, DM, DZ, EC, EE, EG, ES, FI, GB, GD,
GE, GH, GM, HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP,
KR, KZ, LA, LC, LK, LR, LS, LT, LU, LV, LY, MA, MD, MG, MK, MN,
MW, MX, MZ, NA, NG, NI, NO, NZ, OM, PG, PH, PL, PT, RO, RS, RU,
SC, SD, SE, SG, SK, SL, SM, SY, TJ, TM, TN, TR, TT, TZ, UA, UG,
US, UZ, VC, VN, ZA, ZM, ZW
RW: AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI, FR, GB, GR, HU, IE,
IS, IT, LT, LU, LV, MC, NL, PL, PT, RO, SE, SI, SK, TR, BF, BJ,
CF, CG, CI, CM, GA, GN, GQ, GW, ML, MR, NE, SN, TD, TG, BW, GH,
GM, KE, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM, ZW, AM, AZ, BY,
KG, KZ, MD, RU, TJ, TM
ABSTRACT:
Chiral arylphosphines Z[(CR3R4)nQP(E)R1R2]m [1, E = electron pair, BH3, H; m.gtoreq.1, Z = mono- or polyvalent organyloxy, organylthio, sulfonyl, amino, amido, alkylene, (hetero)arylene; n = 0, 1; R3, R4 = H, C1-4 alkyl(oxy), optionally forming a (hetero)cycle; Q = optionally annulated and substituted o-phenylene, (hetero)arylene; R1 .noteq. R2; R1, R2 = H, halo, optionally substituted C1-18 alkyl(oxy), C5-7 cycloalkyl, C6-14 (hetero)aryl(oxy)], transition metal complexes of the phosphines 1 of the type MpLq(X1)r(Sv)s(Sv')s'Ht (3, M = Rh, Ru, Ir, Co, Pd, Pt, Ni, Cu; L = ligand 1, E = electron pair; Sv, Sv' = aqua, MeOH, EtOH, amine, 1,2-diamine, Py, ketone, THF, DMSO, amide, alkene, diene, nitrile, arene, aryl; p = 1, 2; q = 0-4; s, s' = 0-2, t = 0-2) useful as catalysts for asym. hydrogenation, hydrosilylation, hydroboration, hydroformylation, alkene isomerization, hydrocyanation, hydrocarboxylation, electrophilic allylation of C:C, C:O or C:N double bonds, were prepd. by nucleophilic arylation of chiral 1,3,2-oxazaphospholidine-borane complexes derived from chiral aminoalcs. with subsequent hydrolytic cleavage of P-N bond, alkylation or arylation followed by addnl. lithiation and further derivatization. In an example, reaction of (2S,4R,5S)-3,4-dimethyl-2,5-diphenyl-1,3,2-oxazaphospholidine-borane complex derived from D-ephedrine with 2-hydroxyphenyllithium sodium salt in THF at -30.degree. gave (RP)-(2-hydroxyphenyl)(phenyl)(2-hydroxy-N,1-dimethyl-2-phenylethylamino)pho sphine-borane (2ab), which was converted to (SP)-chloro(2-hydroxyphenyl)(phenyl)phosphine-borane (3'a), which was then methylated by MeLi to give the P-chiral phosphine-borane Ph(2-HOC6H4)MeP.cntdot.BH3 (4a). In another examples, hydrogenation of .alpha.-acetamidoacrylic acid, catalyzed by rhodium complexes of the invented phosphines, gave the corresponding N-acetylalanine with 100% conversion and 98-99.6% ee.
Updated 5/15/2007 1:29:51 PM
