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1.
The experimental and computational mechanistic details of the Pd(OAc)(2)/TEA-catalyzed aerobic alcohol oxidation system are disclosed. Measurement of various kinetic isotope effects and the activation parameters as well as rate law derivation support rate-limiting deprotonation of the palladium-coordinated alcohol. Rate-limiting deprotonation of the alcohol is contrary to the majority of related kinetic studies for Pd-catalyzed aerobic oxidation of alcohols, which propose rate-limiting beta-hydride elimination. This difference in the rate-limiting step is supported by the computational model, which predicts the activation energy for deprotonation is 3 kcal/mol higher than the activation energy for beta-hydride elimination. The computational features of the similar Pd(OAc)(2)/pyridine system were also elucidated. Details of the study illustrate that the use of TEA results in an active catalyst that has only one ligand bound to the Pd, resulting in a significant lowering of the activation energy for beta-hydride elimination and, therefore, a catalyst that is active at room temperature.  相似文献   

2.
The mechanistic details of aerobic alcohol oxidation with catalytic Pd(IiPr)(OAc)(2)(H(2)O) (IiPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) are disclosed. Under optimal conditions, beta-hydride elimination is rate-limiting supported by kinetic studies including a high primary kinetic isotope effect (KIE) value of 5.5 +/- 0.1 and a Hammett rho value of -0.48 +/- 0.04. On the basis of these studies, a late transition state is proposed for beta-hydride elimination, which is further corroborated by theoretical calculations using density functional theory. Additive acetic acid modulates the rates of both the alcohol oxidation sequence and regeneration of the Pd catalyst. With no additive [HOAc], turnover-limiting reprotonation of intermediate palladium peroxo is kinetically competitive with beta-hydride elimination, allowing for reversible oxygenation and decomposition of Pd(0). With additive [HOAc] (>2 mol %), reprotonation of the palladium peroxo is fast and beta-hydride elimination is the single rate-controlling step. This proposal is supported by an apparent decomposition pathway modulated by [HOAc], a change in alcohol concentration dependence, a lack of [O(2)] dependence at high [HOAc], and significant changes in the KIE values at different HOAc concentrations.  相似文献   

3.
Wang L  Floreancig PE 《Organic letters》2004,6(23):4207-4210
Heating allylic and homoallylic alcohols and 2-pyridylmethyl formate in the presence of Ru(3)(CO)(12) initiates a tandem sequence of hydroesterification and lactonization. Mechanistic studies suggest that regioselectivity and overall reaction efficiency are governed by the relative rates of reductive elimination and beta-hydride elimination for the alkylruthenium intermediates.  相似文献   

4.
Pd(OAc)(2):pyridine (1:4) is an efficient catalyst system for the oxidation of alcohols with molecular oxygen. A mechanistic study of this reaction reveals that pyridine promotes the aerobic oxidation of palladium(0) but inhibits the oxidation of alcohol by palladium(II). Kinetic results reveal that turnover-limiting substrate oxidation consists of (i) formation of a palladium(II)-alkoxide, (ii) pyridine dissociation, and (iii) beta-hydride elimination. These results provide a framework for the design and/or screening of more effective aerobic oxidation catalysts.  相似文献   

5.
The reaction of a palladiumII-hydride species with molecular oxygen to form palladiumII-hydroperoxide has been proposed as a key step in Pd-catalyzed aerobic oxidation reactions. We recently reported one of the first experimental precedents for such a step (Angew. Chem., Int. Ed. 2006, 45, 2904-2907). DFT calculations have been used to probe the mechanism for this reaction, which consists of formal insertion of O2 into the palladium-hydride bond of trans-(NHC)2Pd(H)OAc (NHC = N-heterocyclic carbene). Four different pathways were considered: (1) hydrogen atom abstraction (HAA) of the Pd-H bond by molecular oxygen, (2) reductive elimination of HX followed by oxygenation of Pd0 and protonolysis of the (eta2-peroxo)-PdII species, (3) oxygenation of palladiumII-hydride with subsequent reductive elimination of the O-H bond from an eta2-peroxo-PdIV center, and (4) formation of a cis-superoxide adduct of the palladium-hydride species followed by O-H bond formation via hydrogen atom migration. The calculations reveal that pathways 1 and 2 are preferred energetically, and both pathways exhibit very similar kinetic barriers. This result suggests that more than one pathway is possible for catalyst reoxidation in Pd-catalyzed aerobic oxidation reactions.  相似文献   

6.
The key interactions responsible for the unique reactivity of (-)-sparteine-PdX(2) complexes (X = chloride, acetate) in the enantioselective oxidation of secondary alcohols have been elucidated using quantum mechanics (B3LYP DFT with the PBF polarizable continuum solvent model). From examining many possible pathways, we find the mechanism involves: (1) substitution of the alcohol in place of an X-group, (2) deprotonation of the bound alcohol by the deposed anion and free sparteine, (3) beta-hydride elimination through a four-coordinate transition state in which the second anion is displaced but tightly associated, (4) replacement of the ketone product with the associated anion. The enantioselectivities observed under base-rich reaction conditions follow directly from calculated energies of diastereomeric beta-hydride elimination transition states incorporating (R) and (S) substrates. This relationship reveals an important role of the anion, namely to communicate the steric interaction of the ligand on one side of the Pd(II) square plane and the substrate on the other side. When no anion is included, no enantioselectivity is predicted. Locating these transition states in different solvents shows that higher dielectrics stabilize the charge separation between the anion and metal and draw the anion farther into solution. Thus, the solvent influences the barrier height (rate) and selectivity of the oxidation.  相似文献   

7.
The reaction of molecular oxygen with a Pd(II)-hydride species to form a Pd(II)-hydroperoxide represents one of the proposed catalyst reoxidation pathways in Pd-catalyzed aerobic oxidation reactions, but well-defined examples of this reaction were discovered only recently. Here, we present a mechanistic study of the reaction of O2 with trans-(IMes) 2Pd(H)(OBz), 1 (IMes = 1,3-dimesitylimidazol-2-ylidene), which yields trans-(IMes) 2Pd(OOH)(OBz), 2. The reaction was monitored by (1)H NMR spectroscopy in benzene-d6, and kinetic studies reveal a two-term rate law, rate = k1[1] + k2[1][BzOH], and a small deuterium kinetic isotope effect, k(Pd-H)/k(Pd-D) = 1.3(1). The rate is independent of the oxygen pressure. The data support a stepwise mechanism for the conversion of 1 into 2 consisting of rate-limiting reductive elimination of BzOH from 1 followed by rapid reaction of molecular oxygen with (IMes) 2Pd(0) and protonolysis of a Pd-O bond of the eta(2)-peroxo complex (IMes) 2Pd(O2). Benzoic acid and other protic additives (H2O, ArOH) catalyze the oxygenation reaction, probably by stabilizing the transition state for reductive elimination of BzOH from 1. This study provides the first experimental validation of the mechanism traditionally proposed for aerobic oxidation of Pd-hydride species.  相似文献   

8.
A partial switch in mechanism for the partial oxidation of alcohols on nickel surfaces can be induced by substitution of gamma-hydrogens with more electronegative fluorine atoms. While exclusive dehydrogenation to acetone via beta-hydride elimination from 2-propoxide surface species is seen with 2-propanol, some dehydration to 3,3,3-trfluoropropene is observed with 1,1,1-trifluoro-2-propanol. The latter reaction involves a gamma-hydride elimination rate-limiting step.  相似文献   

9.
The mechanistic details of the Pd(II)/(-)-sparteine-catalyzed aerobic oxidative kinetic resolution of secondary alcohols were elucidated, and the origin of asymmetric induction was determined. Saturation kinetics were observed for rate dependence on [(-)-sparteine]. First-order rate dependencies were observed for both the Pd((-)-sparteine)Cl(2) concentration and the alcohol concentration at high and low [(-)-sparteine]. The oxidation rate was inhibited by addition of (-)-sparteine HCl. At low [(-)-sparteine], Pd-alkoxide formation is proposed to be rate limiting, while at high [(-)-sparteine], beta-hydride elimination is proposed to be rate determining. These conclusions are consistent with the measured kinetic isotope effect of k(H)/k(D) = 1.31 +/- 0.04 and a Hammett rho value of -1.41 +/- 0.15 at high [(-)-sparteine]. Calculated activation parameters agree with the change in the rate-limiting step by increasing [(-)-sparteine] with DeltaH(++) = 11.55 +/- 0.65 kcal/mol, DeltaS(++) = -24.5 +/- 2.0 eu at low [(-)-sparteine], and DeltaH(++) = 20.25 +/- 0.89 kcal/mol, DeltaS() = -5.4 +/- 2.7 eu at high [(-)-sparteine]. At high [(-)-sparteine], the selectivity is influenced by both a thermodynamic difference in the stability of the diastereomeric Pd-alkoxides formed and a kinetic beta-hydride elimination to maximize asymmetric induction. At low [(-)-sparteine], the selectivity is influenced by kinetic deprotonation, resulting in lower k(rel) values. A key, nonintuitive discovery is that (-)-sparteine plays a dual role in this oxidative kinetic resolution of secondary alcohols as a chiral ligand on palladium and as an exogenous chiral base.  相似文献   

10.
Quantum mechanics calculations (B3LYP and MPW1K density functional theory) on mechanisms relevant to the Wacker process for dehydrogenation of alcohol to ketone show that the commonly accepted mechanism for product formation (beta-hydride elimination (BHE) leading to Pd-H formation) is not energetically feasible (36.2 kcal/mol). An alterative pathway involving a five-bodied reductive elimination (RE) leads to an activation enthalpy of 18.8 kcal/mol, which is just half that of the BHE from the -OH group usually assumed for the Wacker process. We find that a water molecule catalyzes both processes, reducing the barrier to 17.2 for RE and 25.0 for BHE, but will not change the relative ordering of the two mechanisms. This suggests that assumptions of BHE mechanisms should be reexamined for cases in which the beta atom is not an alkyl group.  相似文献   

11.
The reductive elimination of 2-hydrocarbyl-imidazolium salts from hydrocarbyl-palladium complexes bearing N-heterocyclic carbene (NHC) ligands represents an important deactivation route for catalysts of this type. We have explored the influence that carbene N-substituents have on both the activation energy and the overall thermodynamics of the reductive elimination reaction using density functional theory (DFT). Given the proximity of the N-substituent to the three-centred transition structure, steric bulk has little influence on the activation barrier and it is electronic factors that dominate the barriers' magnitude. Increased electron donation from the departing NHC ligand acts to stabilise the associated complex against reductive elimination, with stability following the trend: Cl < H < Ph < Me < Cy < iPr < neopentyl < tBu. The intimate involvement of the carbene p pi-orbital in determining the barrier to reductive elimination means N-substituents that are capable of removing pi-density (e.g. phenyl) act to promote a more facile reductive elimination.  相似文献   

12.
The Pd(OAc)(2)/pyridine catalyst system is one of the most convenient and versatile catalyst systems for selective aerobic oxidation of organic substrates. This report describes the catalytic mechanism of Pd(OAc)(2)/pyridine-mediated oxidation of benzyl alcohol, which has been studied by gas-uptake kinetic methods and (1)H NMR spectroscopy. The data reveal that turnover-limiting substrate oxidation by palladium(II) proceeds by a four-step pathway involving (1) formation of an adduct between the alcohol substrate and the square-planar palladium(II) complex, (2) proton-coupled ligand substitution to generate a palladium-alkoxide species, (3) reversible dissociation of pyridine from palladium(II) to create a three-coordinate intermediate, and (4) irreversible beta-hydride elimination to produce benzaldehyde. The catalyst resting state, characterized by (1)H NMR spectroscopy, consists of an equilibrium mixture of (py)(2)Pd(OAc)(2), 1, and the alcohol adduct of this complex, 1xRCH(2)OH. These in situ spectroscopic data provide direct support for the mechanism proposed from kinetic studies. The catalyst displays higher turnover frequency at lower catalyst loading, as revealed by a nonlinear dependence of the rate on [catalyst]. This phenomenon arises from a competition between forward and reverse reaction steps that exhibit unimolecular and bimolecular dependences on [catalyst]. Finally, overoxidation of benzyl alcohol to benzoic acid, even at low levels, contributes to catalyst deactivation by formation of a less active palladium benzoate complex.  相似文献   

13.
A zwitterionic palladium complex [[Ph(2)BP(2)]Pd(THF)(2)][OTf] (1) (where [Ph(2)BP(2)] = [Ph(2)B(CH(2)PPh(2))(2)](-)) reacts with trialkylamines to activate a C-H bond adjacent to the amine N atom, thereby producing iminium adduct complexes [Ph(2)BP(2)]Pd(N,C:eta(2)-NR(2)CHR'). In all cases examined the amine activation process is selective for the secondary C-H bond position adjacent to the N atom. These palladacycles undergo facile beta-hydride elimination/olefin reinsertion processes as evident from deuterium scrambling studies and chemical trap studies. The kinetics of the amine activation process was explored, and beta-hydride elimination appears to be the rate-limiting step. A large kinetic deuterium isotope effect for the amine activation process is evident. The reaction profile in less polar solvents such as benzene and toluene is different at room temperature and leads to dimeric [[Ph(2)BP(2)]Pd](2) (4) as the dominant palladium product. Low-temperature toluene-d(8) experiments proceed more cleanly, and intermediates assigned as [Ph(2)BP(2)]Pd(NEt(3))(OTf) and the iminium hydride species [[Ph(2)BP(2)]Pd(H)(Et(2)N=CHCH(3))][OTf] are directly observed. The complex (Ph(2)SiP(2))Pd(OTf)(2) (14) was also studied for amine activation and generates dimeric [(Ph(2)SiP(2))Pd](2)[OTf](2) (16) as the dominant palladium product. These collective data are discussed with respect to the mechanism of the amine activation and, in particular, the influence that solvent polarity and charge have on the overall reaction profile.  相似文献   

14.
Bulky biaryl phosphine ligands facilitate Pd-catalyzed C-O coupling reactions of aryl halides with primary and secondary alcohols by promoting reductive elimination at the expense of beta-hydride elimination. The key to their success is the ability to match the size of the ligand to that of the combination of substrates. The efficient coupling of a number of unactivated aryl chlorides and bromides with cyclic and acyclic secondary alcohols was achieved. This included the coupling of allylic alcohols for the first time in a Pd-catalyzed coupling process.  相似文献   

15.
Benzylic, allylic, and aliphatic alcohols are oxidized to aldehydes and ketones in a reaction catalyzed by Keggin-type polyoxomolybdates, PV(x)Mo(12-x)O(40)(-(3+x)) (x = 0, 2), with DMSO as a solvent. The oxidation of benzylic alcohols is quantitative within hours and selective, whereas that of allylic alcohols is less selective. Oxidation of aliphatic alcohols is slower but selective. Further mechanistic studies revealed that, for H(3)PMo(12)O(40) as a catalyst and benzylic alcohols as substrates, the sulfoxide is in fact an oxygen donor in the reaction. Postulated reaction steps as determined from isotope-labeling experiments, kinetic isotope effects, and Hammett plots include (a) sulfoxide activation by complexation to the polyoxometalate and (b) oxygen transfer from the activated sulfoxide and elimination of water from the alcohol. The mechanism is supported by the reaction kinetics.  相似文献   

16.
DFT methods were used to elucidate features of coordination environment of Pd(II) that could enable Ar-F reductive elimination as an elementary C-F bond-forming reaction potentially amenable to integration into catalytic cycles for synthesis of organofluorine compounds with benign stoichiometric sources of F(-). Three-coordinate T-shaped geometry of Pd(II)Ar(F)L (L = NHC, PR(3)) was shown to offer kinetics and thermodynamics of Ar-F elimination largely compatible with synthetic applications, whereas coordination of strong fourth ligands to Pd or association of hydrogen bond donors with F each caused pronounced stabilization of Pd(II) reactant and increased activation barrier beyond the practical range. Decreasing donor ability of L promotes elimination kinetics via increasing driving force and para-substituents on Ar exert a sizable SNAr-type TS effect. Synthesis and characterization of the novel [Pd(C(6)H(4)-4-NO(2))ArL(mu-F)](2) (L = P(o-Tolyl)(3), 17; P(t-Bu)(3), 18) revealed stability of the fluoride-bridged dimer forms of the requisite Pd(II)Ar(F)L as the key remaining obstacle to Ar-F reductive elimination in practice. Interligand steric repulsion with P(t-Bu)(3) served to destabilize dimer 18 by 20 kcal/mol, estimated with DFT relative to PMe(3) analog, yet was insufficient to enable formation of greater than trace quantities of Ar-F; C-H activation of P(t-Bu)(3) followed by isobutylene elimination was the major degradation pathway of 18 while Ar/F- scrambling and Ar-Ar reductive elimination dominated thermal decomposition of 17. However, use of Buchwald's L = P(C(6)H(4)-2-Trip)(t-Bu)(2) provided the additional steric pressure on the [PdArL(mu-F)](2) core needed to enable formation of aryl-fluoride net reductive elimination product in quantifiable yields (10%) in reactions with both 17 and 18 at 60 degrees over 22 h.  相似文献   

17.
The oxidative addition products trans-[Pd(NHC)(2)(Ar)Cl] (NHC = cyclo-C[N(t)BuCH](2); Ar = Me-4-C(6)H(4), MeO-4-C(6)H(4), CO(2)Me-4-C(6)H(4)) have been isolated in good yields from the reactions of ArCl with the amination precatalyst [Pd(NHC)(2)] and structurally characterized. The former undergo reversible dissociation of one NHC ligand at elevated temperatures, and a value of 25.57 kcal mol(-1) has been determined for the Pd-NHC dissociation enthalpy in the case where Ar = Me-4-C(6)H(4). Detailed kinetic studies have established that the oxidative addition reactions proceed by a dissociative mechanism. Rate data for the oxidation addition of Me-4-C(6)H(4)Cl to [Pd(NHC)(2)] compared to that obtained for the [Pd(NHC)(2)]-catalyzed coupling of morpholine with 4-chlorotoluene are consistent with a rate-determining oxidative addition in the catalytic amination reaction. The relative rates of oxidative addition of the three aryl chlorides to [Pd(NHC)(2)] (CO(2)Me-4-C(6)H(4)Cl > Me-4-C(6)H(4)Cl > MeO-4-C(6)H(4)Cl) reflect the electronic nature of the substituents and also parallel observed trends in coupling efficiency for these aryl halides in aminations.  相似文献   

18.
This paper reports the synthesis and characterization of a variety of ruthenium complexes coordinated with phosphine and N-heterocyclic carbene (NHC) ligands. These complexes include several alkylidene derivatives of the general formula (NHC)(PR(3))(Cl)(2)Ru=CHR', which are highly active olefin metathesis catalysts. Although these catalysts can be prepared adequately by the reaction of bis(phosphine) ruthenium alkylidene precursors with free NHCs, we have developed an alternative route that employs NHC-alcohol or -chloroform adducts as "protected" forms of the NHC ligands. This route is advantageous because NHC adducts are easier to handle than their free carbene counterparts. We also demonstrate that sterically bulky bis(NHC) complexes can be made by reaction of the pyridine-coordinated precursor (NHC)(py)(2)(Cl)(2)Ru=CHPh with free NHCs or NHC adducts. Two crystal structures are presented, one of the mixed bis(NHC) derivative (H(2)IMes)(IMes)(Cl)(2)Ru=CHPh, and the other of (PCy(3))(Cl)(CO)Ru[eta(2)-(CH(2)-C(6)H(2)Me(2))(N(2)C(3)H(4))(C(6)H(2)Me(3))], the product of ortho methyl C-H bond activation. Other side reactions encountered during the synthesis of new ruthenium alkylidene complexes include the formation of hydrido-carbonyl-chloride derivatives in the presence of primary alcohols and the deprotonation of ruthenium vinylcarbene ligands by KOBu(t). We also evaluate the olefin metathesis activity of NHC-coordinated complexes in representative RCM and ROMP reactions.  相似文献   

19.
Iridium-catalyzed borylation of benzene with diboron was theoretically investigated with the DFT method, where an iridium(I) boryl complex, Ir(Beg)(NN) 1, and an iridium(III) tris(boryl) complex, Ir(Beg)(3)(NN) 14, (eg (ethyleneglycolato) = -OCH(2)CH(2)O-, NN = HN=CHCH=NH (diim) or 2,2'-bipyridine (bpy)) were adopted as models of active species and B(2)(eg)(2) was adopted as a model of bis(pinacolato)diboron (pinacolato = -OCMe(2)CMe(2)O-). Oxidative addition of a benzene C-H sigma-bond to 1 takes place with an activation barrier (E(a)) of 11.2 kcal/mol, followed by reductive elimination of phenylborane, Ph-Beg, from Ir(Beg)(H)(Ph)(diim) with an activation barrier of 15.6 kcal/mol. Though the oxidative addition and the reductive elimination occur with moderate activation barriers, B(2)(eg)(2) much more easily reacts with 1 to afford 14 than does benzene, of which the activation barrier is very small (2.9 kcal/mol). Oxidative addition of the benzene C-H sigma-bond to 14 occurs with a moderate activation barrier of 24.2 kcal/mol to afford an unusual seven-coordinate iridium(V) complex, Ir(H)(Ph)(Beg)(3)(bpy) 16. From this complex, phenylborane Ph-Beg is produced through the reductive elimination with concomitant formation of IrH(Beg)(2)(bpy) 17, where the activation barrier is 4.9 kcal/mol. Complex 17 further reacts with diboron to form Ir(H)(Beg)(4)(bpy) (E(a) = 8.0 kcal/mol), followed by the reductive elimination of borane H-Beg (E(a) = 2.6 kcal/mol) to regenerate Ir(Beg)(3)(bpy), when diboron exists in excess in the reaction solution. After consumption of diboron, IrH(Beg)(2)(bpy) reacts with borane, H-Beg, to form Ir(H)(2)(Beg)(3) (E(a) = 21.3 kcal/mol) followed by the reductive elimination of H(2), to regenerate Ir(Beg)(3)(bpy) with concomitant formation of H(2). Formation of the iridium(III) tris(boryl) complex 14 from IrCl(diim) and diboron was also theoretically investigated; IrCl(diim) undergoes two steps of oxidative addition of diboron to afford a seven-coordinate iridium(V) complex, IrCl(Beg)(4)(NN), from which the reductive elimination of Cl-Beg takes place easily to afford 14. From these results, it should be clearly concluded that the iridium(III) tris(boryl) complex is an active species and an unusual iridium(V) species is involved as a key intermediate in the reaction. Detailed discussion is presented on the full catalytic cycle and the importance of a seven-coordinate iridium(V) intermediate.  相似文献   

20.
Panne P  DeAngelis A  Fox JM 《Organic letters》2008,10(14):2987-2989
A Rh-catalyzed procedure for the cyclopropanation of alkenes with alpha-alkyl-alpha-diazoesters is described. With dirhodium tetraoctanoate, the predominant pathway is beta-hydride elimination. While a number of sterically demanding carboxylate ligands serve to avoid beta-hydride elimination, it was found that triphenylacetate (TPA) also imparts high diastereoselectivity.  相似文献   

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