Difluorphos, an electron-poor diphosphane: A good match between electronic and steric features

被引:233
作者
Jeulin, S
de Paule, SB
Ratovelomanana-Vidal, V
Genet, JP
Champion, N
Dellis, P
机构
[1] Ecole Natl Super Chim Paris, Lab Synth Select Organ & Prod Nat, F-75231 Paris 05, France
[2] SYNKEM SAS, F-21301 Chenove, France
关键词
asymmetric catalysis; atropisomerism; fluorinated ligands; hydrogenation; ruthenium;
D O I
10.1002/anie.200352453
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The π acidity makes the difference: The fluorinated diphosphane, difluorphos, is synthesized (see structure: purple = P, red = O, green = F, gray = C) and its stereoelectronic features are evaluated in theoretical and experimental studies. Its unusual π acidity explains the excellent results obtained with it in ruthenium-mediated asymmetric hydrogenation of fluorinated β-functionalized ketones. These results are better than those obtained with other biphenyl-based diphosphanes.
引用
收藏
页码:320 / 325
页数:6
相关论文
共 51 条
[1]  
Allen D. W., 1982, J CHEM SOC DA, V51
[2]   Synthesis, resolution, and applications of 2,2′-bis(diphenylphosphino)-3,3′-binaphtho[2,1-b]furan [J].
Andersen, NG ;
Parvez, M ;
Keay, BA .
ORGANIC LETTERS, 2000, 2 (18) :2817-2820
[3]  
[Anonymous], [No title captured], Patent No. [EP 0850945, 0850945]
[4]   (DIPHENYLPHOSPHINO)-BIHETEROARYLS - THE FIRST EXAMPLE OF A NEW CLASS OF CHIRAL ATROPISOMERIC CHELATING DIPHOSPHINE LIGANDS FOR TRANSITION-METAL-CATALYZED STEREOSELECTIVE REACTIONS [J].
BENINCORI, T ;
BRENNA, E ;
SANNICOLO, F ;
TRIMARCO, L ;
ANTOGNAZZA, P ;
CESAROTTI, E .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1995, (06) :685-686
[5]   3,3′-bis(diphenylphosphino)-1,1′-disubstituted-2,2′-biindoles:: Easily accessible, electron-rich, chiral diphosphine ligands for homogeneous enantioselective hydrogenation of oxoesters [J].
Benincori, T ;
Piccolo, O ;
Rizzo, S ;
Sannicolò, F .
JOURNAL OF ORGANIC CHEMISTRY, 2000, 65 (24) :8340-8347
[6]   2,2′,5,5′-tetramethyl-4,4′-bis(diphenylphoshino)-3,3′-bithiophene:: A new, very efficient, easily accessible, chiral biheteroaromatic ligand for homogeneous stereoselective catalysis [J].
Benincori, T ;
Cesarotti, E ;
Piccolo, O ;
Sannicolò, F .
JOURNAL OF ORGANIC CHEMISTRY, 2000, 65 (07) :2043-2047
[7]   New class of chiral diphosphine ligands for highly efficient transition metal-catalyzed stereoselective reactions: The bis(diphenylphosphino) five-membered biheteroaryls [J].
Benincori, T ;
Brenna, E ;
Sannicolo, F ;
Trimarco, L ;
Antognazza, P ;
Cesarotti, E ;
Demartin, F ;
Pilati, T .
JOURNAL OF ORGANIC CHEMISTRY, 1996, 61 (18) :6244-6251
[8]   Asymmetric synthesis of fluorinated β-hydroxy esters via ruthenium-mediated hydrogenation [J].
Blanc, D ;
Ratovelomanana-Vidal, V ;
Gillet, JP ;
Genêt, JP .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2000, 603 (01) :128-130
[9]   Selective hydrogenation for fine chemicals: Recent trends and new developments [J].
Blaser, HU ;
Malan, C ;
Pugin, B ;
Spindler, F ;
Steiner, H ;
Studer, M .
ADVANCED SYNTHESIS & CATALYSIS, 2003, 345 (1-2) :103-151
[10]   Synthesis and molecular modeling studies of SYNPHOS®, a new, efficient diphosphane ligand for ruthenium-catalyzed asymmetric hydrogenation [J].
de Paule, SD ;
Jeulin, S ;
Ratovelomanana-Vidal, V ;
Genêt, JP ;
Champion, N ;
Dellis, P .
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2003, 2003 (10) :1931-1941