Meta-analysis in asymmetric catalysis. Influence of chelate geometry on the roles of PN chelating ligands

被引:15
作者
Carroll, Michael. R. [1 ]
Guiry, Patrick J. [1 ]
Brown, John M. [2 ]
机构
[1] Univ Coll Dublin, Ctr Synth & Chem Biol, Sch Chem & Chem Biol, Dublin 4, Ireland
[2] Univ Oxford, Dept Chem, Chem Res Lab, Oxford OX1 3TA, England
关键词
CATALYZED ENANTIOSELECTIVE DIBORATION; ATROPISOMERIC PHOSPHINAMINE LIGAND; CHIRAL CATALYSTS; (PHOSPHANYLOXAZOLINE)PALLADIUM COMPLEXES; TRANSFER HYDROGENATION; ALLYLIC ALKYLATIONS; NMR INVESTIGATIONS; RHODIUM COMPLEXES; PLANAR CHIRALITY; PALLADIUM;
D O I
10.1039/c3ob40360b
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
All X-ray structures of PN ligands forming 6-ring metal complex chelates have been retrieved from the CDS database, and those lacking chelate chirality filtered out. Many of the remainder fit naturally into four main families (PPFA, FcPhox, Phox and Quinap), which have been widely applied to asymmetric catalysis in diverse ways. It is known through experimental observation that certain of these ligand structures are more effective for specific classes of reaction but there has been little by way of explanation for their divergent behaviour. In this paper we examine the wide variation of conformations within individual families of PN complexes in the solid state, establish common features, and make cross-correlations with their effectiveness in specific catalytic asymmetric reactions. The extent of rigidity in the chelate varies widely and yet flexible complexes may be extremely effective in asymmetric catalysis. These observations emphasise the importance of induced fit between reactants and catalyst and militate against over-reliance on rigid lock-and-key models.
引用
收藏
页码:4591 / 4601
页数:11
相关论文
共 92 条
[1]   Pd-Catalyzed asymmetric allylic alkylations using various diphenylphosphino(oxazolinyl)ferrocene ligands [J].
Ahn, KH ;
Cho, CW ;
Park, JW ;
Lee, SW .
TETRAHEDRON-ASYMMETRY, 1997, 8 (08) :1179-1185
[2]   SYNTHESIS AND RESOLUTION OF 1-(2-DIPHENYLPHOSPHINO-1-NAPHTHYL)ISOQUINOLINE - A P-N CHELATING LIGAND FOR ASYMMETRIC CATALYSIS [J].
ALCOCK, NW ;
BROWN, JM ;
HULMES, DI .
TETRAHEDRON-ASYMMETRY, 1993, 4 (04) :743-756
[3]  
Amoroso D, 2008, ALDRICHIM ACTA, V41, P15
[4]   Ruthenium(II)-catalyzed asymmetric transfer hydrogenation of ketones using chiral oxazolinylferrocenylphosphines and one of their Ru(II) complex [J].
Arikawa, Y ;
Ueoka, M ;
Matoba, K ;
Nishibayashi, Y ;
Hidai, M ;
Uemura, S .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1999, 572 (02) :163-168
[5]   The enantioselective Tsuji allylation [J].
Behenna, DC ;
Stoltz, BM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (46) :15044-15045
[6]   Enantioselective Decarboxylative Alkylation Reactions: Catalyst Development, Substrate Scope, and Mechanistic Studies [J].
Behenna, Douglas C. ;
Mohr, Justin T. ;
Sherden, Nathaniel H. ;
Marinescu, Smaranda C. ;
Harned, Andrew M. ;
Tani, Kousuke ;
Seto, Masaki ;
Ma, Sandy ;
Novak, Zoltan ;
Krout, Michael R. ;
McFadden, Ryan M. ;
Roizen, Jennifer L. ;
Enquist, John A., Jr. ;
White, David E. ;
Levine, Samantha R. ;
Petrova, Krastina V. ;
Iwashita, Akihiko ;
Virgil, Scott C. ;
Stoltz, Brian M. .
CHEMISTRY-A EUROPEAN JOURNAL, 2011, 17 (50) :14199-14223
[7]   Atroposelective biaryl coupling with chiral catalysts: Total synthesis of the antileishmanial naphthylisoquinoline alkaloids ancistrotanzanine B and ancistroealaine A [J].
Bringmann, G ;
Hamm, A ;
Schraut, M .
ORGANIC LETTERS, 2003, 5 (16) :2805-2808
[8]   MECHANISTIC AND SYNTHETIC STUDIES IN CATALYTIC ALLYLIC ALKYLATION WITH PALLADIUM COMPLEXES OF 1-(2-DIPHENYLPHOSPHINO-1-NAPHTHYL)ISOQUINOLINE [J].
BROWN, JM ;
HULMES, DI ;
GUIRY, PJ .
TETRAHEDRON, 1994, 50 (15) :4493-4506
[9]   ASYMMETRIC CATALYZES .5. ENANTIOSELECTIVE AMINO-ACID SYNTHESIS BY HYDROGENATION OF PROCHIRAL OLEFINS WITH RH-COMPLEXES OF THE NEW OPTICALLY-ACTIVE CHELATING PHOSPHANE NORPHOS [J].
BRUNNER, H ;
PIERONCZYK, W ;
SCHONHAMMER, B ;
STRENG, K ;
BERNAL, I ;
KORP, J .
CHEMISCHE BERICHTE-RECUEIL, 1981, 114 (03) :1137-1149
[10]   Synthesis of (R,R)-. and (S,S)-Norphos [J].
Brunner, Henri ;
Muschiol, Manfred ;
Zabel, Manfred .
SYNTHESIS-STUTTGART, 2008, 3 (03) :405-408