Characteristic monomials with chirality fittingness for combinatorial enumeration of isomers with chiral and achiral ligands

A new method of combinatorial enumeration based on characteristic monomials with chirality fittingness (CM-CFs) has been proposed in order to enumerate isomers with chiral ligands as well as with achiral ones. The CM-CFs have been defined as monomials that consist of three kinds of dummy variables in light of the subduction of the Q-conjugacy representations for chiral and achiral cyclic groups. A procedure of calculating CM-CFs for cyclic groups and finite groups has been discribed so as to tabulate them as CM-CF tables. Then the CM-CF method has been applied to the enumeration of isomers with achiral ligands as well as chiral ones.     

Planar chiral ferrocene salen-type ligands featuring additional central and axial chirality

We report on novel chiral tridentate [NO₂]H₂ and tetradentate [N₂O₂]H₂ Schiff base ligands containing a planar chiral ferrocene moiety linked to hydroxyl-imine or diimine donors with central or axial chirality. Structurally, these ligands resemble half-salen and salen systems designed for stereoselective applications of their transition metal complexes in homogeneous catalysis. The modular synthesis involves diastereoselective metalation of chiral ferrocene or pentamethylferrocene acetals, followed by stereoconservative hydroxyalkylation and condensation with chiral hydroxyamines or diamines, respectively. In comparison to salen-type systems, an important advantage of these ligands is their tunable steric protection of the alkoxide donor site. A total of 18 different ligands varying in electronic and steric properties have been prepared and fully characterized by NMR, IR, mass spectroscopy and by single crystal structure analysis of nine precursors and representatives.     

Point chirality functions,symmetry rules for chiral representations in one-centre molecular and field models

There are many problems (e.g. intermolecular forces, molecule-radiation field interactions) in which the separate entities (molecules, photons, or sources of static fields) many be represented by point moments (electric and magnetic. permanent or transition). Such point models lead to expressions containing moment products, which reduce on averaging to orientation-independent product functions that are characteristic of the species and its moment representation. Those functions that change sign when the chirality of the system is changed may be referred to as point chirality functions. In this paper, the point chirality functions generated from a given set of moments are defined, and in turn yield the conditions under which a given moment set is chiral; i.e. gives a chiral representation of the species it represents. They are shown to constitute a set of transferable parameters that lead to a unified approach to orientationally averaged chiral interactions of various kinds. By determining the point chirality functions of isolated chiral systems, the results are applied to interactions between various combinations of molecular, static field and radiation field systems without the need of considering the forms of each interaction in detail.     

Importance of planar chirality in chiral catalysts with three chiral elements: the role of planar chirality in 2'-substituted 1,1'-P,N-ferrocene ligands on the enantioselectivity in Pd-catalyzed allylic substitution.

A series of novel planar chiral 2'-substituted 1,1'-P,N-ferrocene ligands 9-11, 14, and 16 were prepared with diastereopurity >99:1 and found to be effective in asymmetric allylic alkylation and amination reactions. Ligand 14 furnished the highest enantiomeric excess, 98.5% and 96.5% ee in alkylation and amination reactions, respectively. The role of planar chirality in asymmetric reactions has been examined, and decisive effects on enantioselectivity as well as the control of absolute configuration in palladium-catalyzed allylic alkylation and amination reactions were observed. To clarify why and how the planar chirality governed the stereochemical outcome, X-ray crystallographic structures of eta(3)-diphenylallyl Pd complexes, (1)H NMR, (31)P NMR spectra of palladium dichloride complexes, and eta(3)-diphenylallyl Pd complexes of three 1,1'-P,N-ferrocene ligands were analyzed with the aid of COSY and 2D NOESY experiments. All results led to the conclusion that planar chirality influences the stereochemical outcome by changing or even inverting the ratio of two rotamers because of the steric interaction between a planar chiral group and the coordination site.     

Novel chiral copper complexes of N,P-ferrocenyl ligands with central and planar chirality as efficient catalyst for asymmetric addition of diethylzinc to imines

A new type of chiral copper complexes of N,P-ferrocenyl ligands with central and planar chirality as efficient catalyst was applied to the enantioselective addition of diethylzinc to N-diphenylphosphinoylimines. The (R)- and (S)-enantiomers of the addition reaction were obtained for this transformation. In the presence of 6 mol % of bidentate ligand 1 and 12 mol % of Cu(OTf)₂, the asymmetric addition process affords N-diphenylphosphinoylamides in up to 97% ee and 95% yields.     

Dinuclear complexes of chiral tetradentate pyridylimine ligands: diastereoselectivity, positive cooperativity, anion selectivity, ligand self-sorting based on chirality, and magnetism

The synthesis and coordination chemistry of two chiral tetradentate pyridylimine Schiff base ligands are reported. The ligands were prepared by the nucleophilic displacement of both bromides of 1,3-bis(bromomethyl)benzene (2) or 3,5-bis(bromomethyl)toluene (3) by the anion of (S)-valinol, followed by capping of both amine groups with pyridine-2-carboxaldehyde. Both ligands react with CoCl(2) and NiCl(2) to give [M(2)L(2)Cl(2)](2+) complexes. Remarkably, neither fluoride nor bromide ions can act as bridging ligands. The formation of [Co(2)((S)-3)(2)Cl(2)](2+) is highly diastereoselective, and X-ray crystallography shows that both metal centers in the [Co(2)((S)-3)(2)Cl(2)](CoCl(4)) complex adopt the lambda configuration (crystal data: [Co(2)(C(31)H(40)N(4)O(2))(2)Cl(2)](CoCl(4)).(CH(3)CN)(3), monoclinic, P2(1), a = 11.595(2) A, b = 22.246(4) A, c = 15.350(2) A, V = 3705(1) A(3), beta = 110.643(3) degrees, Z = 2). Structurally, the dinuclear complex can be viewed as a helicate with the helical axis running perpendicular to the [Co(2)Cl(2)] plane. The reaction of racemic 2 with CoCl(2) was shown by (1)H NMR spectroscopy to yield a racemic mixture of Lambda,Lambda-[Co(2)((S)-2)(2)Cl(2)](2+) and delta,delta-[Co(2)((R)-2)(2)Cl(2)](2+) complexes; that is, a homochiral recognition process takes place. Spectrophotometric titrations were performed by titrating (S)-3 with Co(ClO(4))(2) followed by Bu(4)NCl, and the global stability constants of [Co((S)-3)](2+) (log beta(110) = 5.7), [Co((S)-3)(2)](2+) (log beta(120) = 11.6), and [Co(2)((S)-3)(2)Cl(2)](2+) (log beta(110) = 23.8) were calculated. The results revealed a strong positive cooperativity in the formation of [Co(2)((S)-3)(2)Cl(2)](2+). Variable-temperature magnetic susceptibility curves for [Co(2)((S)-2)(2)Cl(2)](BPh(4))(2) and [Co(2)((S)-3)(2)Cl(2)](BPh(4))(2) are very similar and indicate that there are no significant magnetic interactions between the cobalt(II) centers.     

Asymmetric catalysis with chiral oxazolidine ligands

Asymmetric catalysis with chiral 1,3-oxazolidine ligands, which have a sterically tunable, rigid structure that can accommodate several chiral centers, has found increasing attention in recent years. This trend is partly due to the intriguing ring topology of oxazolidines and the prospect of modular synthesis of a diverse set of ligands from a wide range of readily available amino alcohols. The general promise and pitfalls of the synthesis of chiral oxazolidines and the success of selected catalysts including pyridinyl and phosphine derivatives in asymmetric alkylations, alkynylations, allylic alkylations, cycloadditions, and aldol reactions is discussed.     

Electronic and structural chirality of prochiral centres in chiral molecules. A non-steric contribution in stereoselective reactions

Prochiral centres of local C_1h symmetry may undergo addition reactions leading to the destruction of the reflection plane and consequently the formation of a new chiral centre. The chirality of the product is determined by whether the attack is from above or below the plane, so that a hypothetically isolated prochiral centre would lead to equal amounts of the two forms of the chiral product. It is shown, however, that prochiral centres in chiral molecules are, strictly speaking, electronically and structurally chiral even prior to addition because of long range electronic coupling between the prochiral centre and the other parts of the molecule. The nature of the perturbations leading to such chirality are derived, and the role of this induced chirality in leading to stereoselectivity (i.e. favoured attack from one side of the plane) discussed.     

Asymmetric autocatalysis of a ferrocene-containing chiral compound with amplification of chirality

Chiral ferrocene-containing pyrimidyl alkanol can be efficiently synthesized via asymmetric autocatalysis as an enantiomerically pure product. Moreover, a remarkable positive nonlinear effect occurs during this autocatalytic reaction. Starting from a nearly racemic seed, it is thus possible to produce a larger amount of the same compound with high ee.     

New chiral phosphoramidite allenylidene complexes of ruthenium obtained with chirality transfer

The synthesis and structural characterization of the first ruthenium phosphoramidite allenylidene complexes that are chiral at the metal are described. The precursor complex [RuCl(Ind)(PPh₃)₂] (Ind = indenyl anion) was reacted with 1 equiv of different chiral phosphoramidite ligands L to give complexes of the general formula [RuCl(Ind)(PPh₃)L]. These complexes are stereogenic at the metal and at the ligand L. One of these complexes was obtained in diastereomeric purity, and was subsequently converted to allenylidene complexes of the general formula [RuCCCR′R(Ind)(PPh₃)L]⁺PF₆ (R = R′ = Ph; R = Ph, R′ = Me) in diastereomeric purity. As shown by X-ray, the chiral information is completely transferred from the precursor complex to the allenylidenes, which is of importance for potential catalytic applications.     

Concerning the theory of chirality functions

Within the scope of the theory of chirality functions, qualitatively complete chirality functions are subject to restrictions concerning both generality and applicability. In contrast thereto, the concept of qualitative supercompleteness results in less restrictive requirements for chirality functions. Consequently, the applicability of qualitatively supercomplete chirality functions is unlimited with respect to the number of ligand kinds. Given this concept, a group theoretical treatment is performed supplying the formal conditions of qualitative supercompleteness. Subsequently a construction rule for qualitiatively supercomplete chirality functions is presented, which is elaborated in detail in the appendix. On combining physical considerations with the requirement of qualitative supercompleteness the resulting chirality functions appear to include all the possible interactions within and/or between ligands and skeleton. From both a mathematical and a physical point of view these chirality functions should be adequate for describing the chiroptical properties of molecules belonging to a given skeletal class. Nevertheless, all the other critical objections to the theory of chirality functions remain.     

Cymantrene-based iminodiamidophosphites: the first phosphite-type ligands with planar chirality

Optically active phosphite-type ligands with planar chirality have been synthesized for the first time. The new cymantrene-based P,N-iminodiamidophosphites demonstrated high enantioselectivity in the Pd-catalyzed allylic substitution of 1,3-diphenylallyl acetate with dimethyl malonate (up to 94% ee), pyrrolidine (up to 78% ee) and sodium para-toluene sulfinate (up to 84% ee).     

Ruthenium complexes with chiral tetradentate imino-sulfoxide ligands

Treatment of 2-(methylsulfinyl)benzaldehyde (1) with ethylenediamine or (1R,2R)-(-)-1,2-diaminocyclohexane afforded N,N'-bis[2-(methylsulfinyl)benzylidene]ethylenediamine (L(1)) or (1R,2R)-N,N'-bis[2-(methylsulfinyl)benzylidene]-1,2-cyclohexanedia mine (L(2)), respectively. Lithiation of 2-bromobenzaldehyde diethylacetal with n-BuLi/TMEDA followed by reaction with (1R,2S,5R)-(-)-menthyl-(S)-p-toluenesulfinate afforded 2-(S)-(p-tolylsulfinyl)benzaldehyde diethyl acetal (2). Deprotection of 2 with pyridinium tosylate followed by condensation with ethylenediamine, (1R,2R)-(-)-diaminocyclohexane, or (S,S)-(+)-diaminocyclohexane afforded N,N'-bis[2-(S)-(p-tolylsulfinyl)benzylidene]ethylenediamine (L(3)), (1R,2R)-N,N'-bis[2-(S)-(p-tolylsulfinyl)benzylidene]-1,2-cyclohexanediamine ((R,R)-L(4)), or (S,S)-N,N'-bis[2-(S)-(p-tolylsulfinyl)benzylidene]-1,2-cyclohexanediamine ((S,S)-L(4)), respectively. Treatment of [Ru(PPh(3))(3)Cl(2)] with L afforded trans-[Ru(L)Cl(2)] [L = L(1) (3), L(2) (4), L(3) (5), (R,R)-L(4) ((R,R)-6), (S,S)-L(4) ((S,S)-6)]. The X-ray structures of (S(S),R(S))-4, (R,R)-6, and (S,S)-6 have been determined. The average Ru-N, Ru-S, and Ru-Cl distances in (S(S),R(S))-4 are 2.063, 2.2301, and 2.4039 A, respectively. The corresponding distances in (R,R)-6 are 2.071, 2.256, and 2.411 A, and those in (S,S)-6, 2.058, 2.2275, and 2.3831 A. Compound 3 exhibited a reversible Ru(III/II) couple at 0.56 V vs Cp(2)Fe(+/0) in CH(2)Cl(2). Treatment of 3 with AgNO(3) in water afforded the aqua compound trans-[Ru(L(1))Cl(H(2)O)][PF(6)] (7), which has been characterized by X-ray crystallography. The Ru-Cl, Ru-O, average Ru-N, and average Ru-S distances in 7 are 2.3733(6), 2.1469(16), 2.071, and 2.2442 A, respectively. Treatment of 3 with AgNO(3) followed by reaction with PPh(3) afforded [Ru(L(1))(PPh(3))(2)][PF(6)](2) (8). Treatment of [Os(PPh(3))(3)Cl(2)] with L(1) resulted in deoxygenation of one sulfoxide group of L(1) and formation of [Os(L(5))Cl(2)(PPh(3))] (9) (L(5) = N-[2-(methylsulfinyl)benzylidene]-N'-[2-(methylthio)benzylididene]ethylenediamine), which has been characterized by X-ray crystallography. The average Os-S(O), Os-N(trans to P), Os-N(trans to S), Os-P, and Os-Cl distances are 2.1931, 2.085, 2.175, 2.3641, and 2.4266 A, respectively.     

Asymmetric Pauson-Khand reaction with chiral, electron-deficient mono- and bis-phosphine ligands

The intermolecular Pauson-Khand reaction between norbornene and dicobalt carbonyl complexes of phenylacetylene substituted with chiral phosphorus ligands has been investigated. High yields (?98%) and enantiomeric excesses of up to 56% have been observed.     

Reactivity of cyclometallated platinum complexes with chiral ligands

The reaction of [Pt₂Me₄(μ-SMe₂)₂] with 3-substituted iminic thiophenes and 2-phenylpyridine gives platinum (II) [C,N] cyclometallated complexes which contain a labile ligand (SMe₂ or CH₃CN). Several platinum (II) complexes have been synthesized by substitution reactions with phosphine or sulfoxide ligands to introduce, in most cases, a second chiral center. The new complexes’ reactions with methyl iodide were subsequently studied and showed results that are dependent on the steric and electronic effects of both the cyclometallated ligand and the ancillary phosphine or sulfoxide ligand. The structure of [PtMe((R)-C₁₀H₇CHMeNCHC₄H₂S)(CH₃CN)], a synthetic precursor, is also reported.