Design and Synthesis of Novel Chiral Dirhodium(II) Carboxylate Complexes for Asymmetric Cyclopropanation Reactions

被引：77

作者：

Adly, Frady G. ^{[2
]}

Gardiner, Michael G. ^{[3
]}

Ghanem, Ashraf ^{[1
]}

机构：

[1] Univ Canberra, Dept Biomed Sci, Canberra, ACT 2601, Australia

[2] Univ Canberra, Canberra, ACT 2601, Australia

[3] Chem Univ Tasmania, Sch Phys Sci, Hobart, Tas 7001, Australia

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2016年 / 22卷 / 10期

关键词：

asymmetric synthesis; carbenoids; chiral catalysis; cyclopropanation; rhodium; ENANTIOSELECTIVE SYNTHESIS; CATALYST; SYMMETRY; CONSTRUCTION; SUBSTITUTION; SELECTIVITY; LIGANDS;

D O I：

10.1002/chem.201504817

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A novel approach to the design of dirhodium(II) tetracarboxylates derived from (S)-amino acid ligands is reported. The approach is founded on tailoring the steric influences of the overall catalyst structure by reducing the local symmetry of the ligand's N-heterocyclic tether. The application of the new approach has led to the uncovering of [Rh-2(S-(PTTL)-P-tert)(4)] as a new member of the dirhodium(II) family with extraordinary selectivity in cyclopropanation reactions. The stereoselectivity of [Rh-2(S-(PTTL)-P-tert)(4)] was found to be comparable to that of [Rh-2(S-PTAD)(4)] (up to >99% ee), with the extra benefit of being more synthetically accessible. Correlations based on X-ray structures to justify the observed enantioinduction are also discussed.

引用

页码：3447 / 3461

页数：15

共 49 条

[1] Rh2(S-1,2-NTTL)4: A Novel Rh2(S-PTTL)4 Analog With Lower Ligand Symmetry for Asymmetric Synthesis of Chiral Cyclopropylphosphonates
Adly, Frady G.
Maddalena, Johncarlo
Ghanem, Ashraf
[J]. CHIRALITY, 2014, 26 (11) : 764 - 774
[2] Chiral Dirhodium(II) Carboxylates and Carboxamidates as Effective Chemzymes in Asymmetric Synthesis of Three-Membered Carbocycles
Adly, Frady G.
Ghanem, Ashraf
[J]. CHIRALITY, 2014, 26 (11) : 692 - 711
[3] [Anonymous], 2005, ANGEW CHEM
[4] Barbour L.J., 2001, J SUPRAMOL CHEM, V1, P189, DOI [DOI 10.1016/S1472-7862(02)00030-8, 10.1016/S1472-7862(02)00030-8]
[5] Rh2(S-PTTL)3TPA-a mixed-ligand dirhodium(II) catalyst for enantioselective reactions of α-alkyl-α-diazoesters
Boruta, David T.
Dmitrenko, Olga
Yap, Glenn P. A.
Fox, Joseph M.
[J]. CHEMICAL SCIENCE, 2012, 3 (05) : 1589 - 1593
[6] Solvent effect on intramolecular hydrogen bonds in push-pull conjugated molecules
Bouchy, A
Rinaldi, D
Rivail, JL
[J]. INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 2004, 96 (03) : 273 - 281
[7] Guide to enantioselective dirhodium(II)-catalyzed cyclopropanation with aryldiazoacetates
Chepiga, Kathryn M.
Qin, Changming
Alford, Joshua S.
Chennamadhavuni, Spandan
Gregg, Timothy M.
Olson, Jeremy P.
Davies, Huw M. L.
[J]. TETRAHEDRON, 2013, 69 (27-28) : 5765 - 5771
[8] Asymmetric cyclopropanations by rhodium(II) N-(arylsulfonyl)prolinate catalyzed decomposition of vinyldiazomethanes in the presence of alkenes. Practical enantioselective synthesis of the four stereoisomers of 2-phenylcyclopropan-1-amino acid
Davies, HML
Bruzinski, PR
Lake, DH
Kong, N
Fall, MJ
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (29) : 6897 - 6907
[9] Enantioselective synthesis of cyclopropylphosphonates containing quaternary stereocenters using a D2-symmetric chiral catalyst Rh2(S-biTISP)2
Davies, HML
Lee, GH
[J]. ORGANIC LETTERS, 2004, 6 (13) : 2117 - 2120
[10] Novel dirhodium tetraprolinate catalysts containing bridging prolinate ligands for asymmetric carbenoid reactions
Davies, HML
Panaro, SA
[J]. TETRAHEDRON LETTERS, 1999, 40 (29) : 5287 - 5290

← 1 2 3 4 5 →