Manganese-Catalyzed Regioselective C-H Lactonization and Hydroxylation of Fatty Acids with H2O2.

Herein, we report the direct selective C-H lactonization of fatty acids (C5-C16), catalyzed by manganese(II) complexes bearing bis-amino-bis-pyridine ligands. The catalyst system uses the environmentally benign hydrogen peroxide as oxidant and exhibits high efficiency (100-200 TON), providing under optimized conditions γ-lactones in 60-90% yields. Remarkably, by changing the reaction conditions, the oxidation of hexanoic acid can be diverted toward formation of δ-caprolactone in up to 67% yield. Furthermore, the possibility of obtaining (ω-1)-hydroxy derivatives from linear C7-C10 acids in up to 48% yields has been demonstrated.

Reactivity vs. Selectivity of Biomimetic Catalyst Systems of the Fe(PDP) Family through the Nature and Spin State of the Active Iron-Oxygen Species.

Catalytic approaches to late-stage creation of new C-O bonds, especially via oxygenation of particular C-H groups in complex organic molecules, provide challenging tools for the synthesis of biologically active compounds and candidate drugs. In the last decade, significant efforts were invested in designing bioinspired iron based catalyst systems, capable of conducting selective oxidations of organic compounds. The key role of the oxygen-transferring high-valent iron-oxygen species in selective oxygenation is now well established; the next logical step would be gaining insight into the factors governing the oxidation chemo- and stereoselectivity, in relation to the peculiarities of their electronic structure, which would allow introducing the desired level of predictability into those catalytic transformations. In this Personal Account we analyze recent data on the reactivity of bioinspired formally oxoiron(V) catalytically active sites toward organic substrates having C=C and C(sp3 )-H groups. While the majority of reported oxoiron(V) active species are low-spin (S=1/2) complexes, the presence of strong electron-donating groups (NR1 R2 ) in the ligand backbone favors the high-spin (S=3/2) ground state. Remarkably, the high-spin perferryl species exhibit higher chemo-, regio-, and stereoselectivity in the oxidations than their low-spin counterparts, thus witnessing the significance of these subtle electronic effects for the selectivity of oxidations conducted by bioinspired catalysts of the Fe(PDP) family.

Low-Spin and High-Spin Perferryl Intermediates in Non-Heme Iron Catalyzed Oxidations of Aliphatic C-H Groups.

The selectivity patterns of iron catalysts of the Fe(PDP) family in aliphatic C-H oxidation with H2 O2 have been studied (PDP=N,N'-bis(pyridine-2-ylmethyl)-2,2'-bipyrrolidine). Cyclohexane, adamantane, 1-bromo-3,7-dimethyloctane, 3,7-dimethyloctyl acetate, (-)-acetoxy-p-menthane, and cis-1,2-dimethylcyclohexane were used as substrates. The studied catalyst systems generate low-spin (S=1/2) oxoiron(V) intermediates or high-spin (S=3/2) oxoiron(V) intermediates, depending on the electron-donating ability of remote substituents at the pyridine rings. The low-spin perferryl intermediates demonstrate lower stability and higher reactivity toward aliphatic C-H groups of cyclohexane than their high-spin congeners, according to the measured self-decay and second-order rate constants k1 and k2 . Unexpectedly, there appears to be no uniform correlation between the spin state of the oxoiron(V) intermediates, and the chemo- and regioselectivity of the corresponding catalyst systems in the oxidation of the considered substrates. This contrasts with the asymmetric epoxidations by the same catalyst systems, in which case the epoxidation enantioselectivity increases when passing from the systems featuring the more reactive low-spin perferryl intermediates to those with their less reactive high-spin congeners.

Palladium aminopyridine complexes catalyzed selective benzylic C-H oxidations with peracetic acid.

Four palladium(ii) complexes with tripodal ligands of the tpa family (tpa = tris(2-pyridylmethyl)amine) have been synthesized and X-ray characterized. These complexes efficiently catalyze benzylic C-H oxidation of various substrates with peracetic acid, affording the corresponding ketones in high yields (up to 100%), at <1 mol% catalyst loadings. Complex [(tpa)Pd(OAc)](PF6) with the least sterically demanding ligand tpa demonstrates the highest substrate conversions and ketone selectivities. Preliminary mechanistic data provide evidence in favor of metal complex-mediated rate-limiting benzylic C-H bond cleavage by an electron-deficient oxidant.

Ethylene polymerization of nickel catalysts with α-diimine ligands: factors controlling the structure of active species and polymer properties.

α-Diimine and related complexes of late transition metals such as palladium and nickel have been attracting continuing interest as single-site catalysts of ethylene homopolymerization to branched polyolefins, having challenging mechanical properties. The state-of-the art catalysts demonstrate promising catalytic activities, and enhanced thermal stabilities, affording polyethylenes with a variable degree of branching and, in addition, are able to incorporate polar co-monomers into polyethylene structures. At the same time, fundamental understanding of the structure-reactivity relationships of such catalysts mostly remains at the phenomenological level, due to the lack of experimental data on the solution structures of intermediates that drive the polymerization process. In this perspective, we discuss recent advances of α-diimine nickel based catalysts of ethylene polymerization, focusing on the relationships between the catalyst structures on the one hand, and their thermal stabilities and properties of the resulting polyethylene, on the other hand. In addition, some intriguing novel mechanistic findings of these catalyst systems are presented.

Chiral Autoamplification Meets Dynamic Chirality Control to Suggest Nonautocatalytic Chemical Model of Prebiotic Chirality Amplification.

Oxidative kinetic resolution of 1-phenylethanol in the presence of manganese complexes, bearing conformationally nonrigid achiral bis-amine-bis-pyridine ligands, in the absence of any exogenous chiral additives, is reported. The only driving force for the chiral discrimination is the small initial enantiomeric imbalance of the scalemic (nonracemic) substrate: the latter dynamically controls the chirality of the catalyst, serving itself as the chiral auxiliary. In effect, the ee of 1-phenylethanol increases monotonously over the reaction course. This dynamic control of catalyst chirality by the substrate has been unprecedented; a consistent kinetic model for this process is presented. The reported catalyzed substrate self-enantioenrichment mechanism is discussed in relation to the problem of prebiotic chirality amplification.

NMR spectroscopic identification of Ni(ii) species formed upon activation of (α-diimine)NiBr2 polymerization catalysts with MAO and MMAO.

The nature of Ni(ii) species formed upon the activation of the Brookhart's α-diimine polymerization pre-catalyst LNiBr2 with MAO and MMAO (L = 1,4-bis-2,4,6-dimethylphenyl-2,3-dimethyl-1,4-diazabuta-1,3-diene) has been established using 1H and 13C NMR spectroscopy. The heterobinuclear ion pair [LNiII(µ-Me)2AlMe2]+[MeMAO]- is observed at the initial stage of the reaction of LNiBr2 with MAO at -40 °C, whereas the ion pair [LNiII-tBu]+[MeMMAO]- predominates at the initial stage of the reaction of LNiBr2 with MMAO under the same conditions. At higher temperatures, both ion pairs transform into a Ni(i) species displaying an axially anisotropic EPR spectrum (g‖ = 2.21, g⊥ = 2.06, A⊥ = 1.06 mT).

Chiral Manganese Aminopyridine Complexes: the Versatile Catalysts of Chemo- and Stereoselective Oxidations with H2 O2.

In the last decade, manganese(II) complexes with N-donor tetradentate aminopyridine ligands emerged as efficient catalysts of enantioselective epoxidation of olefins and direct selective oxidation of C-H groups in complex organic molecules, with environmentally benign oxidant hydrogen peroxide. In this personal account, we summarize the progress of these catalysts with regard to ligands design, structure-reactivity correlations, evaluation of the substrate scope, as well as mechanistic studies, shedding light on the nature of active sites and the mechanisms of selective oxygenations. Several practically promising catalytic syntheses with the aid of Mn aminopyridine catalysts are exemplified.

Direct Selective Oxidative Functionalization of C-H Bonds with H2O2: Mn-Aminopyridine Complexes Challenge the Dominance of Non-Heme Fe Catalysts.

Non-heme iron(II) complexes are widespread synthetic enzyme models, capable of conducting selective C-H oxidation with H2O2 in the presence of carboxylic acid additives. In the last years, structurally similar manganese(II) complexes have been shown to catalyze C-H oxidation with similarly high selectivity, and with much higher efficiency. In this mini-review, recent catalytic and mechanistic data on the selective C-H oxygenations with H2O2 in the presence of manganese complexes are overviewed. A distinctive feature of catalyst systems of the type Mn complex/H2O2/carboxylic is the existence of two alternative reaction pathways (as found for the oxidation of cumenes), one leading to the formation of alcohol, and the other to ester. The mechanisms of formation of the alcohol and the ester are briefly discussed.

Titanium Salan/Salalen Complexes: The Twofaced Janus of Asymmetric Oxidation Catalysis.

Optically pure chiral epoxides and sulfoxides are ubiquitous building blocks in fine organic synthesis, employed in the pharmaceutical, agrochemical, and cosmetic industries. On the road to chiral epoxides and sulfoxides, efficient and stereoselective transition metal-based catalysts are the most promising guides. Among transition metals, we favor titanium for its cheapness and availability, nontoxicity, and well-known ability to catalyze a variety of stereoselective transformations, including oxidations with environmentally benign H2O2. In this personal account, we summarize the state-of-the-art of rational design of chiral titanium(IV) salan and salalen catalysts, and investigations of their catalytic reactivities and stereoselectivities in the epoxidations of olefins and oxidations of thioethers, unraveling the peculiarities and mechanisms of their catalytic action.

Titanium salan catalysts for the asymmetric epoxidation of alkenes: steric and electronic factors governing the activity and enantioselectivity.

A new insight into the highly enantioselective (up to >99.5 % ee) epoxidation of olefins in the presence of chiral titanium(IV) salan complexes is reported. A series of 14 chiral ligands with varying steric and electronic properties have been designed, and it was found that electronic effects modulate the catalytic activity (without affecting the enantioselectivity), whereas the steric properties account for the enantioselectivity of the epoxidation. Competitive oxidations of p-substituted styrenes reveal the electrophilic nature of the oxygen-transferring active species, with a Hammett ρ value of -0.51; the enantioselectivity is unaffected by the electron-donating (or withdrawing) ability of the p-substituents. Mechanistic studies provide evidence in favor of a stepwise reaction mechanism: in the first (rate-determining) stage, olefin most probably coordinates to the active species, followed by intramolecular enantioselective oxygen transfer. The enantioselectivity increases with decreasing temperature. The modified Eyring plots for the epoxidation of styrene and (Z)-ß-methylstyrene are linear, indicating a single, enthalpy-controlled mechanism of stereoselectivity, with ΔΔH(≠) =-6.6 kJ mol(-1) and -5.4 kJ mol(-1) , respectively.

Formation and evolution of chain-propagating species upon ethylene polymerization with neutral salicylaldiminato nickel(II) catalysts.

Formation of Ni-polymeryl propagating species upon the interaction of three salicylaldiminato nickel(II) complexes of the type [(N,O)Ni(CH3 )(Py)] (where (N,O)=salicylaldimine ligands, Py=pyridine) with ethylene (C2 H4 /Ni=10:30) has been studied by (1) H and (13) C NMR spectroscopy. Typically, the ethylene/catalyst mixtures in [D8 ]toluene were stored for short periods of time at +60 °C to generate the [(N,O)Ni(polymeryl)] species, then quickly cooled, and the NMR measurements were conducted at -20 °C. At that temperature, the [(N,O)Ni(polymeryl)] species are stable for days; diffusion (1) H NMR measurements provide an estimate of the average length of polymeryl chain (polymeryl=(C2 H4 )n H, n=6-18). At high ethylene consumptions, the [(N,O)Ni(polymeryl)] intermediates decline, releasing free polymer chains and yielding [(N,O)Ni(Et)(Py)] species, which also further decompose to form the ultimate catalyst degradation product, a paramagnetic [(N,O)2 Ni(Py)] complex. In [(N,O)2 Ni(Py)], the pyridine ligand is labile (with activation energy for its dissociation of (12.3±0.5) kcal mol(-1) , ΔH(≠) 298 =(11.7±0.5) kcal mol(-1) , ΔS(≠) 298 =(-7±1) cal K(-1) mol(-1) ). Upon the addition of nonpolar solvent (pentane), the pyridine ligand is lost completely to yield the crystals of diamagnetic [(N,O)2 Ni] complex. NMR spectroscopic analysis of the polyethylenes formed suggests that the evolution of chain-propagating species ends up with formation of polyethylene with predominately internal and terminal vinylene groups rather than vinyl groups.

Formation of trivalent zirconocene complexes from ansa-zirconocene-based olefin-polymerization precatalysts: an EPR- and NMR-spectroscopic study.

Reduction of Zr(IV) metallocenium cations with sodium amalgam (NaHg) produces EPR signals assignable to Zr(III) metallocene complexes. The chloro-bridged heterodinuclear ansa-zirconocenium cation [(SBI)Zr(µ-Cl)2AlMe2](+) (SBI = rac-dimethylsilylbis(1-indenyl)), present in toluene solution as its B(C6F5)4(-) salt, thus gives rise to an EPR signal assignable to the complex (SBI)Zr(III)(µ-Cl)2AlMe2, while (SBI)Zr(III)-Me and (SBI)Zr(III)(µ-H)2Al(i)Bu2 are formed by reduction of [(SBI)Zr(µ-Me)2AlMe2](+) B(C6F5)4(-) and [(SBI)Zr(µ-H)3(Al(i)Bu2)2](+) B(C6F5)4(-), respectively. These products can also be accessed, along with (SBI)Zr(III)-(i)Bu and [(SBI)Zr(III)](+) AlR4(-), when (SBI)ZrMe2 is allowed to react with HAl(i)Bu2, eliminating isobutane en route to the Zr(III) complex. Further studies concern interconversion reactions between these and other (SBI)Zr(III) complexes and reaction mechanisms involved in their formation.

Highly efficient, regioselective, and stereospecific oxidation of aliphatic C-H groups with H2O2, catalyzed by aminopyridine manganese complexes.

Aminopyridine manganese complexes [LMn(II)(OTf)(2)] having a similar coordination topology catalyze the oxidation of unactivated aliphatic C-H groups with H(2)O(2), demonstrating excellent efficiency (up to TON = 970), site selectivity, and stereospecificity (up to >99%).

The origin of living polymerization with an o-fluorinated catalyst: NMR spectroscopic characterization of chain-carrying species.

To characterize the origin of living polymerization with nonmetallocene titanium-based catalysts containing o-fluoroaryl substituents, ethene polymerization by an o-fluorinated bis(enolatoimine) titanium catalyst and its nonfluorinated counterpart has been studied by multinuclear NMR spectroscopy by using methylaluminoxane (MAO) or AlMe(3)/CPh(3)B(C(6)F(5))(4) as activators. Formation of ion pairs of the type [TiL(2)Me][MeMAO] and [TiL(2)Me][B(C(6)F(5))(4)] has been observed for both catalysts. These ion pairs react with ethene to afford the chain-propagating species [TiL(2)P][MeMAO] and [TiL(2)P][B(C(6)F(5))(4)], respectively (P = growing polymeryl chain). For the o-F-substituted catalyst species of the second type, NMR spectroscopy provides evidence that the o-F substituents interact with the metal center. This interaction is proposed to keep the polymerization catalysis living by suppressing chain transfer to AlMe(3) and ß-hydrogen transfer processes.

EPR, 1H and 2H NMR, and reactivity studies of the iron-oxygen intermediates in bioinspired catalyst systems.

Complexes [(BPMEN)Fe(II)(CH(3)CN)(2)](ClO(4))(2) (1, BPMEN = N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)-1,2-diaminoethane) and [(TPA)Fe(II)(CH(3)CN)(2)](ClO(4))(2) (2, TPA = tris(2-pyridylmethyl)amine) are among the best nonheme iron-based catalysts for bioinspired oxidation of hydrocarbons. Using EPR and (1)H and (2)H NMR spectroscopy, the iron-oxygen intermediates formed in the catalyst systems 1,2/H(2)O(2); 1,2/H(2)O(2)/CH(3)COOH; 1,2/CH(3)CO(3)H; 1,2/m-CPBA; 1,2/PhIO; 1,2/(t)BuOOH; and 1,2/(t)BuOOH/CH(3)COOH have been studied (m-CPBA is m-chloroperbenzoic acid). The following intermediates have been observed: [(L)Fe(III)(OOR)(S)](2+), [(L)Fe(IV)═O(S)](2+) (L = BPMEN or TPA, R = H or (t)Bu, S = CH(3)CN or H(2)O), and the iron-oxygen species 1c (L = BPMEN) and 2c (L = TPA). It has been shown that 1c and 2c directly react with cyclohexene to yield cyclohexene oxide, whereas [(L)Fe(IV)═O(S)](2+) react with cyclohexene to yield mainly products of allylic oxidation. [(L)Fe(III)(OOR)(S)](2+) are inert in this reaction. The analysis of EPR and reactivity data shows that only those catalyst systems which display EPR spectra of 1c and 2c are able to selectively epoxidize cyclohexene, thus bearing strong evidence in favor of the key role of 1c and 2c in selective epoxidation. 1c and 2c were tentatively assigned to the oxoiron(V) intermediates.

Nonheme manganese-catalyzed asymmetric oxidation. A Lewis acid activation versus oxygen rebound mechanism: evidence for the "third oxidant".

The catalytic properties of a series of chiral nonheme aminopyridinylmanganese(II) complexes [LMn(II)(OTf)(2)] were investigated. The above complexes were found to efficiently catalyze enantioselective olefin oxidation to the corresponding epoxides with different oxidants (peroxycarboxylic acids, alkyl hydroperoxides, iodosylarenes, etc.) with high conversions and selectivities (up to 100%) and enantiomeric excesses (up to 79%). The effect of the ligand structure on the catalytic performance was probed. Epoxidation enantioselectivities were found to be strongly dependent on the structure of the oxidants (performic, peracetic, and m-chloroperbenzoic acids; tert-butyl and cumyl hydroperoxides; iodosylbenzene and iodosylmesitylene), thus bearing evidence that the terminal oxidant molecule is incorporated in the structure of the oxygen-transferring intermediates. High-valence electron-paramagnetic-resonance-active manganese complexes [LMn(IV)═O](2+) and [LMn(IV)(µ-O)(2)Mn(III)L](3+) were detected upon interaction of the starting catalyst with the oxidants. The high-valence complexes did not epoxidize styrene and could themselves only contribute to minor olefin oxidation sideways. However, the oxomanganese(IV) species were found to perform the Lewis acid activation of the acyl and alkyl hydroperoxides or iodosylarenes to form the new type of oxidant [oxomanganese(IV) complex with a terminal oxidant], with the latter accounting for the predominant enantioselective epoxidation pathway in the nonheme manganese-catalyzed olefin epoxidations.

EPR spectroscopic trapping of the active species of nonheme iron-catalyzed oxidation.

The key intermediate of a bioinspired iron catalyst for selective hydrocarbon oxidation based on hydrogen peroxide and an iron complex with a tetradentate aminopyridine ligand was trapped by EPR. On the basis of EPR and reactivity data this intermediate is tentatively proposed to be an oxoiron(V) complex.

Iron-catalyzed oxidation of thioethers by iodosylarenes: stereoselectivity and reaction mechanism.

Catalytic properties of a series of iron(III)-salen (salen=N,N'-bis(salicylidene)ethylenediamine dianion) and related complexes in asymmetric sulfoxidation reactions, with iodosylarenes as terminal oxidants, have been explored. These catalysts have been found to efficiently catalyze oxidation of alkyl aryl sulfides to sulfoxides with high chemoselectivity (up to 100 %) and moderate-to-high enantioselectivity (up to 84 % with isopropylthiobenzene and iodosylmesitylene), the TON (TON=turnover number) approaching 500. The influence of the ligand (electronic and steric effects of the substituents), oxidant, and substrate structures on the oxidation stereoselectivity has been investigated systematically. The structure of the reactive intermediates (complexes of the type [Fe(III)(ArIO)(salen)] and the reaction mechanism have been revealed by both mechanistic studies with different iodosylarenes and direct in situ (1)H NMR observation of the formation of the reactive species and its reaction with the substrate.