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An efficient procedure for the enantioselective synthesis of beta-ferrocenyl-beta-amino alcohols, a new class of central chiral ferrocene derivatives suitable for the elaboration of auxiliaries and ligands for asymmetric synthesis, is described. Key steps of the method are the catalytic asymmetric dihydroxylation of 1-ferrocenyl alkenes and the regio- and stereoselective azide substitution of the hydroxyl group adjacent to the ferrocene moiety. The stereochemistry of the substitution step has been established by X-ray diffraction analysis of a cyclic derivative. The first catalytic enantioselective synthesis of a beta-ferrocenyl-beta-amino acid derivative is also disclosed.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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The structures adopted by a range of poly(pyrazolyl)borate complexes [ML2Tpx] [M = Rh, Ir; L2 = diene; Tp x = Bp? {dihydrobis(3,5-dimethylpyrazolyl)borate}, Tp? {hydrotris(3,5-dimethylpyrazolyl)borate}, Tp {hydrotris(pyrazolyl)borate}, B(pz)4 {tetrakis(pyrazolyl)borate}] have been investigated. Low steric hindrance between ligands in [Rh(eta-nbd)Tp] (nbd = norbornadiene), [Rh(eta-cod)Tp] (cod = cycloocta-1,5-diene) and [Rh(eta-nbd)Tp?] results in kappa3 coordination of the pyrazolylborate but [M(eta-cod)Tp?] (M = Rh, Ir) are kappa2 coordinated with the free pyrazolyl ring positioned above and approximately parallel to the square plane about the metal. All but the most sterically hindered Tp x complexes undergo fast exchange of the coordinated and uncoordinated pyrazolyl rings on the NMR spectroscopic timescale. For [Rh(eta-cod){B(pz)4}], [Rh(eta-dmbd)Tp?] (dmbd = 2,3-dimethylbuta-1,3-diene) and [Rh(eta-cod)TpPh] {TpPh = hydrotris(3-phenylpyrazolyl)borate} the fluxional process is slowed at low temperatures so that inequivalent pyrazolyl rings are observed. The bonding modes of the Tp? ligand (but not of other pyrazolylborate ligands) can be determined by 11B NMR and IR spectroscopy. The 11B chemical shifts (for a series of Tp? complexes) show the general pattern, kappa3 < -7.5 ppm < kappa2 and the nu(BH) stretch kappa3 > 2500 cm-1 > kappa2. The electrochemical behaviour of the pyrazolylborate complexes is related to the degree of structural change which occurs on electron transfer. One-electron oxidation of complexes with Tp?, Tp and B(pz)4 ligands is generally reversible although that of [Ir(eta-cod)Tp] is only reversible at higher scan rates and that of [Ir(eta-cod){B(pz)4}] is irreversible. Of the complexes with the more sterically hindered TpPh ligand, only [Rh(eta-nbd)TpPh] shows any degree of reversible oxidation. The ESR spectra of a range of Rh(ii) complexes show coupling to both 14N and 103Rh nuclei in most cases but what appears to be coupling to rhodium and one hydrogen atom, possibly a hydride ligand, for the oxidation product of [Rh(eta-nbd)TpPh]. The Royal Society of Chemistry 2008.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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The water-soluble iridium complex {Cp*[6,6′-(OH)2bpy] (H2O)}[OTf]2 (Cp=nu5-pentamethylcyclopentadienyl, bpy=2,2′-bipyridine) was found to be a general and highly efficient catalyst for the Nalkylation of the poor nucleophilic sulfonamides with alcohols as alkylating agents in water. The presence of OH units in the bpy ligand is crucially important for the catalytic activity of the iridium complex. Mechanistic investigations revealed that the catalytically active species is a ligand-metal bifunctional iridium complex bearing an N,N’-chelated 2,2′-bipyridinated ligand and an aqua ligand. Notably, the present catalytic system and the proposed mechanism provide a new horizon and scope for the development of “hydrogen autotransfer (or hydrogen-borrowing) processes”.

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Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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A novel C[dbnd]N bond forming strategy based on oxo/imido heterometathesis between N-sulfinylamines and ketones, catalyzed by a well-defined silica-supported Ti imido complex, was applied to prepare a series of hardly accessible 1,1?-diacetylferrocene ketimines.

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These cats are purrfectionists: The ChenPhos ligands (see structure) showed dramatically higher catalytic activity in the title reaction than their C 2-symmetric predecessor with two dimethylaminoethyl-substituted ferrocenyl(phenyl)phosphanyl groups. The ready accessibility, extreme air stability, and high enantioselectivity, activity, and productivity of these ligands make them very promising for a wide range of practical applications. Copyright

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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The invention discloses a carbamate compounds containing ferrocene group and its synthesis method, which belongs to the field of high molecular. The invention also discloses a containing ferrocene group of the carbamate compound preparation method. The invention containing ferrocene group a carbamate compound, chemical quality good stability, has a plurality of catalytic characteristics; for lubricating oil additive, at the same time has good oxidation resistance, abrasion resistance and corrosion resistance; for fuel oil additive, with smoke combustion-supporting, the advantages of reducing pollution. (by machine translation)

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Chemical engineers ensure the efficiency and safety of chemical processes, adapt the chemical make-up of products to meet environmental or economic needs, and apply new technologies to improve existing processes. Product Details of 1293-65-8. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. Introducing a new discovery about 1293-65-8, Name is 1,1′-Dibromoferrocene

The Pd-catalyzed cross-coupling reaction between halobenzenes and ferrocene-1,1′-diboronic acid is reported.Condensation proceeds smoothly to give 1,1′-diphenyl- and 1,1′-bis(halophenyl)-substituted ferrocenes bearing fluoro, chloro and bromo substituents in good yields.An effective synthesis of the intermediate ferrocene-1,1′-diboronic acid is described.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Novel redox-active polyferrocenyl transition metal dithiocarbamate macrocyclic molecular boxes (10a-c), (11) and (12a-c) are synthesised by reaction of the respective ferrocenyl secondary amines, namely, N,N?-bis(ferrocenemethyl)-1,3-bis(aminomethyl)benzene (4), 1,1?-bis(benzylaminomethyl)ferrocene (8) and 1,1?-bis((ferrocenylmethyl)aminomethyl)ferrocene (9) with carbon disulfide, potassium hydroxide and transition metal (zinc, copper, nickel) acetate in high yields (52-82%) and characterised by spectroscopic and electrochemical techniques. The single-crystal X-ray structure of 10a shows that each zinc atom is in tetrahedral geometry, being bonded to two dithiocarbamate ligands with Zn-S distances 2.32(1)-2.44(1) A.

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Aromatic and (hetero)aromatic chromium aminocarbenes were lithiated on the (hetero)aromatic ring and transmetalated with ZnBr2. The subsequent Pd(PPh3)4- or PdCl2(XantPhos)-catalyzed Negishi reaction with dibromoarenes or chromium alkoxy-/aminocarbenes bearing bromine atoms yielded bisaminocarbene or mixed bisalkoxyaminocarbene complexes of chromium. This methodology allows easy access to the biscarbene complexes containing poly(hetero)aromatic bridges, such as biphenylene, bithienylene, tetrathienylene, 1,1?-ferrocenylene, and others. In total, 18 new biscarbene complexes, including two containing both chromium and tungsten, were synthesized in this fashion. The electrochemical behavior of the biscarbenes obtained exhibits electronic communication between the metals.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion