Syntheses of Families of Enantiopure and Diastereopure Cobalt Catalysts Derived from Trications of the Formula [Co(NH2CHArCHArNH2)3]3.
作者： Subrata K. Ghosh , Kyle G. Lewis , Anil Kumar , John A. Gladysz
DOI: 10.1021/ACS.INORGCHEM.6B03042
关键词:
摘要: Aerobic reactions of CoX2 (X = OAc, Cl) or Co(ClO4)2 with (S,S)-1,2-diphenylethylenediamine [(S,S)-dpen] in CH3OH, followed by HCl HClO4 additions, give the diastereomeric lipophobic salts Λ-[Co((S,S)-dpen)3]3+3Cl– [Λ-(S,S)-13+3Cl–] Δ-(S,S)-13+3ClO4– (60–65%) high degrees selectivity. Anion metatheses (room temperature) and equilibrations (charcoal, 70 °C) show that former is more stable than Δ-(S,S)-13+3Cl–, latter Λ-(S,S)-13+3ClO4–. Additional anion lead to large families lipophilic Λ- Δ-(S,S)-13+2X–X′– [X/X′ Cl/BArf [BArf B(3,5-C6H3(CF3)2)4], PF6/BArf, BF4/BArf, PhBF3/BArf, Cl/BArf20 [BArf20 B(C6F5)4], BArf/BArf, BArf20/BArf20, BF4/BF4, PF6/PF6]. Mixed formula Δ-[Co((S,S)-NH2CHArCHArNH2)3]3+2Cl–BArf– are similarly prepared (Ar 4-C6H4n-Bu, 4-C6H4Cl, 4-C6H4CF3, 4-C6H4OCH3, α-naphthyl, β-naphthyl, 2-C6H4OBn). The diastereotopic NHH′ protons exhibit different 1H NMR signals; one shifts far downfield whe...
acs.org
sci-hub.se 参考文章(41)
Haohua Huo, Chen Fu, Chuanyong Wang, Klaus Harms, Eric Meggers, Metal-templated enantioselective enamine/H-bonding dual activation catalysis Chemical Communications. ,vol. 50, pp. 10409- 10411 ,(2014) , 10.1039/C4CC04636F
William R. Robinson, Perchlorate salts of metal ion complexes: Potential explosives Journal of Chemical Education. ,vol. 62, pp. 1001- ,(1985) , 10.1021/ED062P1001
R.D. Gillard, Configurations of 1,2-diamines Tetrahedron. ,vol. 21, pp. 503- 506 ,(1965) , 10.1016/S0040-4020(01)82221-3
Cristina García-Simón, Rafael Gramage-Doria, Saeed Raoufmoghaddam, Teodor Parella, Miquel Costas, Xavi Ribas, Joost N. H. Reek, Enantioselective Hydroformylation by a Rh-Catalyst Entrapped in a Supramolecular Metallocage Journal of the American Chemical Society. ,vol. 137, pp. 2680- 2687 ,(2015) , 10.1021/JA512637K
P. L. Fereday, S. F. Mason, The dynamic-coupling basis of the conformational optical activity of chelated metal complexes Journal of The Chemical Society D: Chemical Communications. pp. 1314- 1315 ,(1971) , 10.1039/C29710001314
Hyunwoo Kim, Yen Nguyen, Cindy Pai-Hui Yen, Leonid Chagal, Alan J. Lough, B. Moon Kim, Jik Chin, Stereospecific synthesis of C2 symmetric diamines from the mother diamine by resonance-assisted hydrogen-bond directed diaza-Cope rearrangement. Journal of the American Chemical Society. ,vol. 130, pp. 12184- 12191 ,(2008) , 10.1021/JA803951U
Reiko Kuroda, Stephen F. Mason, Crystal structure and absolute configuration of (+)-tris[(–)-1,2-diphenylethylenediamine]cobalt(III) nitrate monohydrate J. Chem. Soc., Dalton Trans.. pp. 1016- 1020 ,(1977) , 10.1039/DT9770001016
D. Sen, W.C. Fernelius, Catalytic racemization of optically active complexes: Tris(ethylenediamine)cobalt(III), -platinum(IV), and -rhodium(III) halides Journal of Inorganic and Nuclear Chemistry. ,vol. 10, pp. 269- 274 ,(1959) , 10.1016/0022-1902(59)80120-2
Ralf Lungwitz, Stefan Spange, A hydrogen bond accepting (HBA) scale for anions, including room temperature ionic liquids New Journal of Chemistry. ,vol. 32, pp. 392- 394 ,(2008) , 10.1039/B714629A
Victor I. Maleev, Michael North, Vladimir A. Larionov, Ivan V. Fedyanin, Tatyana F. Savel'yeva, Margarita A. Moscalenko, Alexander F. Smolyakov, Yuri N. Belokon, Chiral Octahedral Complexes of Cobalt(III) as “Organic Catalysts in Disguise” for the Asymmetric Addition of a Glycine Schiff Base Ester to Activated Olefins Advanced Synthesis & Catalysis. ,vol. 356, pp. 1803- 1810 ,(2014) , 10.1002/ADSC.201400091