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1.
The ruthenium‐ and rhodium‐catalyzed oxidative spiroannulation of naphthols and phenols with alkynes was investigated by means of density functional theory calculations. The results show that the reaction undergoes O?H deprotonation/C(sp2)?H bond cleavage through a concerted metalation–deprotonation mechanism/migratory insertion of the alkyne into the M?C bond to deliver the eight‐membered metallacycle. However, the dearomatization through the originally proposed enol–keto tautomerization/C?C reductive elimination was calculated to be kinetically inaccessible. Alternatively, an unusual metallacyclopropene, generated from the isomerization of the eight‐membered metallacycle through rotation of the C?C double bond, was identified as a key intermediate to account for the experimental results. The subsequent C?C coupling between the carbene carbon atom and the carbon atom of the 2‐naphthol/phenol ring was calculated to be relatively facile, leading to the formation of the unexpected dearomatized products. The calculations reproduce quite well the experimentally observed formal [5+2] cycloaddition in the rhodium‐catalyzed oxidative annulation of 2‐vinylphenols with alkynes. The calculations show that compared with the case of 2‐alkenylphenols, the presence of conjugation effects and less steric repulsion between the phenol ring and the vinyl moiety make the competing reductive oxyl migration become dominant, which enables the selectivity switch from the spiroannulation to the formal [5+2] cycloaddition.  相似文献   

2.
The B3LYP density functional studies on the dirhodium tetracarboxylate-catalyzed C-H bond activation/C-C bond formation reaction of a diazo compound with an alkane revealed the energetics and the geometry of important intermediates and transition states in the catalytic cycle. The reaction is initiated by complexation between the rhodium catalyst and the diazo compound. Driven by the back-donation from the Rh 4d(xz) orbital to the C[bond]N sigma*-orbital, nitrogen extrusion takes place to afford a rhodium[bond]carbene complex. The carbene carbon of the complex is strongly electrophilic because of its vacant 2p orbital. The C[bond]H activation/C[bond]C formation proceeds in a single step through a three-centered hydride transfer-like transition state with a small activation energy. Only one of the two rhodium atoms works as a carbene binding site throughout the reaction, and the other rhodium atom assists the C[bond]H insertion reaction. The second Rh atom acts as a mobile ligand for the first one to enhance the electrophilicity of the carbene moiety and to facilitate the cleavage of the rhodium[bond]carbon bond. The calculations reproduce experimental data including the activation enthalpy of the nitrogen extrusion, the kinetic isotope effect of the C[bond]H insertion, and the reactivity order of the C[bond]H bond.  相似文献   

3.
A metal‐containing N‐heterocyclic germylene based on a N‐mesityl (Mes)‐substituted oxalamidine framework is reported. The precursor (MesN=)2C–C(–N(H)Mes)2 ( 1 H2) was converted into its rhodium complex [Rh(κ2N‐ 1 H2)(cod)][OTf] ( 2 ) (cod = 1,5‐cyclooctadiene; OTf = triflate) in 62 % isolated yield. Subsequent reaction of 2 with Ge{N(SiMe3)2}2 gave the crystalline N‐heterocyclic germylene [Rh(cod)(μ‐ 1 )Ge][OTf] ( 3 ) in 50 % yield. The compounds under study were fully characterized by various methods, also including X‐ray crystallographic studies on single crystals of 2 and 3 . Density functional theory (DFT) calculations revealed that π conjugation in the bridging oxalamidine framework is increased and n(N)–p(Ge) π bonding is decreased upon κ2N metal coordination; a further weakening of the Ge–N bond occurs through triflate coordination to the GeII atom. Nevertheless, preliminary coordination studies revealed that 3 behaves as 2‐electron (L ‐type) germylene donor ligand. Treatment of 3 with [Ir(cod)Cl]2 furnished the heterobimetallic complex [Rh(cod)(μ‐ 1 )Ge‐Ir(cod)Cl][OTf] ( 4 ), as evidenced by NMR spectroscopic investigations and DFT calculations.  相似文献   

4.
A rhodium(II)‐ or copper(I)‐catalyzed formal intramolecular carbene insertion into vinylic C(sp2)−H bonds is reported herein. This method provides straightforward access to 1H ‐indenes with high efficiency and excellent functional‐group compatibility. Mechanistically, the reaction is proposed to involve the following sequence: metal carbene formation, intramolecular nucleophilic addition of the double bond to the electron‐deficient carbene carbon atom, dearomatization, and finally a 1,5‐H shift.  相似文献   

5.
A rhodium‐catalyzed intramolecular acetyl‐group transfer has been achieved through a “cut and sew” process. The challenge arises from the existence of different competitive pathways. Preliminary success has been achieved with unstrained enones that contain a biaryl linker. The use of an electron‐rich N‐heterocycilc carbene (NHC) ligand is effective to inhibit undesired β‐hydrogen elimination. Various 9,10‐dihydrophenanthrene derivatives can be prepared with excellent functional‐group compatibility. The 13C‐labelling study suggests that the reaction begins with cleavage of the unstrained C?C bond, followed by migratory insertion and reductive elimination.  相似文献   

6.
A general regioselective rhodium‐catalyzed head‐to‐tail dimerization of terminal alkynes is presented. The presence of a pyridine ligand (py) in a Rh–N‐heterocyclic‐carbene (NHC) catalytic system not only dramatically switches the chemoselectivity from alkyne cyclotrimerization to dimerization but also enhances the catalytic activity. Several intermediates have been detected in the catalytic process, including the π‐alkyne‐coordinated RhI species [RhCl(NHC)(η2‐HC?CCH2Ph)(py)] ( 3 ) and [RhCl(NHC){η2‐C(tBu)?C(E)CH?CHtBu}(py)] ( 4 ) and the RhIII–hydride–alkynyl species [RhClH{? C?CSi(Me)3}(IPr)(py)2] ( 5 ). Computational DFT studies reveal an operational mechanism consisting of sequential alkyne C? H oxidative addition, alkyne insertion, and reductive elimination. A 2,1‐hydrometalation of the alkyne is the more favorable pathway in accordance with a head‐to‐tail selectivity.  相似文献   

7.
The activation of carbon–fluorine (C?F) bonds is an important topic in synthetic organic chemistry. Metal‐mediated and ‐catalyzed elimination of β‐ or α‐fluorine proceeds under milder conditions than oxidative addition to C?F bonds. The β‐ or α‐fluorine elimination is initiated from organometallic intermediates having fluorine substituents on carbon atoms β or α to metal centers, respectively. Transformations through these elimination processes (C?F bond cleavage), which are typically preceded by carbon–carbon (or carbon–heteroatom) bond formation, have been increasingly developed in the past five years as C?F bond activation methods. In this Minireview, we summarize the applications of transition‐metal‐mediated and ‐catalyzed fluorine elimination to synthetic organic chemistry from a historical perspective with early studies and from a systematic perspective with recent studies.  相似文献   

8.
New isocyanide ligands with meta‐terphenyl backbones were synthesized. 2,6‐Bis[3,5‐bis(trimethylsilyl)phenyl]‐4‐methylphenyl isocyanide exhibited the highest rate acceleration in rhodium‐catalyzed hydrosilylation among other isocyanide and phosphine ligands tested in this study. 1H NMR spectroscopic studies on the coordination behavior of the new ligands to [Rh(cod)2]BF4 indicated that 2,6‐bis[3,5‐bis(trimethylsilyl)phenyl]‐4‐methylphenyl isocyanide exclusively forms the biscoordinated rhodium–isocyanide complex, whereas less sterically demanding isocyanide ligands predominantly form tetracoordinated rhodium–isocyanide complexes. FTIR and 13C NMR spectroscopic studies on the hydrosilylation reaction mixture with the rhodium–isocyanide catalyst showed that the major catalytic species responsible for the hydrosilylation activity is the Rh complex coordinated with the isocyanide ligand. DFT calculations of model compounds revealed the higher affinity of isocyanides for rhodium relative to phosphines. The combined effect of high ligand affinity for the rhodium atom and the bulkiness of the ligand, which facilitates the formation of a catalytically active, monoisocyanide–rhodium species, is proposed to account for the catalytic efficiency of the rhodium–bulky isocyanide system in hydrosilylation.  相似文献   

9.
A RhI‐catalyzed three‐component reaction of tert‐propargyl alcohol, diazoester, and alkyl halide has been developed. This reaction can be considered as a carbene‐involving sequential alkyl and alkynyl coupling, in which C(sp)? C(sp3) and C(sp3)? C(sp3) bonds are built successively on the carbenic carbon atom. The RhI‐carbene migratory insertion of an alkynyl moiety and subsequent alkylation are proposed to account for the two separate C? C bond formations. This reaction provides an efficient and tunable method for the construction of all‐carbon quaternary center.  相似文献   

10.
It has been established that an electron-deficient cyclopentadienyl rhodium(III) (CpERhIII) complex catalyzes the oxidative and decarboxylative [2+1+2+1] cycloaddition of benzoic acids with diynes through C≡C triple bond cleavage, leading to fused naphthalenes. This cyclotrimerization is initiated by directed ortho C−H bond cleavage of a benzoic acid, and the subsequent regioselective alkyne insertion and decarboxylation produce a five-membered rhodacycle. The electron-deficient nature of the CpERhIII complex promotes reductive elimination giving a cyclobutadiene–rhodium(I) complex rather than the second intermolecular alkyne insertion. The oxidative addition of the thus generated cyclobutadiene to rhodium(I) (formal C≡C triple bond cleavage) followed by the second intramolecular alkyne insertion and reductive elimination give the corresponding [2+1+2+1] cycloaddition product. The synthetic utility of the present [2+1+2+1] cycloaddition was demonstrated in the facile synthesis of a donor–acceptor [5]helicene and a hemi-hexabenzocoronene by a combination with the chemoselective Scholl reaction.  相似文献   

11.
Cyclic (amino)(aryl)carbenes (CAArCs) result from the replacement of the alkyl substituent of cyclic (alkyl)(amino) carbenes (CAACs) by an aryl group. This structural modification leads to enhanced electrophilicity of the carbene center with retention of the high nucleophilicity of CAACs, and therefore CAArCs feature a small singlet–triplet gap. The isoindolium precursors are readily prepared in good yields, and deprotonation at low temperature, in the presence of [RhCl(cod)]2 and [(Me2S)AuCl] lead to air‐stable rhodium and gold CAArC‐supported complexes, respectively. The rhodium complexes promote the [3+2] cycloaddition of diphenylcyclopropenone with ethyl phenylpropiolate, and induce the addition of 2‐vinylpyridine to alkenes by CH activation. The gold complexes allow for the catalytic three‐component preparation of 1,2‐dihydroquinolines from aniline and phenyl acetylene. These preliminary results illustrate the potential of CAArC ligands in transition‐metal catalysis.  相似文献   

12.
Rhodium(I)‐catalyzed cyclization of allenynes with a tethered carbonyl group was investigated. An unusual insertion of a C?O bond into the C(sp2)–rhodium bond of a rhodacycle intermediate occurs via a highly strained transition state. Direct reductive elimination from the obtained rhodacyle intermediate proceeds to give a tricyclic product containing an 8‐oxabicyclo[3.2.1]octane skeleton, while β‐hydride elimination from the same intermediate gives products that contain fused five‐ and seven‐membered rings in high yields.  相似文献   

13.
Six new [RhBr(NHC)(cod)] (NHC = N‐heterocyclic carbene; cod = 1,5‐cyclooctadiene) type rhodium complexes ( 4–6 ) have been prepared by the reaction of [Rh(μ‐OMe)(cod)]2 with a series of corresponding imidazoli(in)ium bromides ( 1–3 ) bearing mesityl (Mes) or 2,4,6‐trimethylbenzyl (CH2Mes) substituents at N1 and N3 positions. They have been fully characterized by 1 H, 13 C and heteronuclear multiple quantum correlation NMR analyses, elemental analysis and mass spectroscopy. Complexes of type [(NHC)RhBr(CO)2] (NHC = imidazol‐2‐ylidene) ( 7b–9b ) were also synthesized to compare σ‐donor/π‐acceptor strength of NHC ligands. Transfer hydrogenation (TH) reaction of acetophenone has been comparatively studied by using complexes 4–6 as catalysts. The symmetrically CH2Mes‐substituted rhodium complex bearing a saturated NHC ligand ( 5a ) showed the highest catalytic activity for TH reaction. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

14.
A systematic theoretical study has been performed on the recently reported RhI‐catalyzed [3+2+2] carbocyclization reactions between alkenylidenecyclopropanes (ACPs) and alkynes. With the aid of theoretical calculations, two possible mechanisms, that is, alkene‐carbometalation‐first and alkyne‐carbometalation‐first mechanisms, are examined in this study. In the oxidative addition step, the possibility of reaction on either the distal or proximal C? C bond of the cyclopropane group has been evaluated. The calculations indicate that the alkene‐activation‐first mechanism is more favored for the overall catalytic cycle. This mechanism involves four steps, that is, oxidative addition of the distal (rather than the proximal) C? C bond of cyclopropane group, alkene carbometalation, alkyne carbometalation, and reductive elimination. The rate‐determining step in the overall catalytic cycle is the carbometalation of the alkyne (i.e., the alkyne‐insertion step) and this step also determines the regioselectivity. Finally, the origin of the regioselectivity is determined by the steric effect (i.e., the steric crowding between the electron‐withdrawing group on alkyne and other ligands on the rhodium center) in the alkyne‐insertion step.  相似文献   

15.
The potential energy profile for the [Rh(R,R)‐Et‐BisP*]+‐catalyzed asymmetric hydrogenation of prochiral enamides, α‐acetamidoacrylonitrile, was studied by the nonlocal density functional method (B3LYP). As illustrated, this hydrogenation is exothermic and goes mainly through association of [Rh(R,R)‐Et‐BisP*]+ with α‐acetamidoacrylonitrile, oxidative addition of hydrogen, migratory insertion of an olefin carbon into a Rh? H bond, reductive elimination of the C? H bond from the alkyl hydride, and dissociation of product–catalyst adducts with regeneration of the catalyst. The turnover‐limiting step for this reaction is the oxidative addition of hydrogen. The main product predicted theoretically is the R‐conformer. Our results are consistent with available empirical data and experiments for rhodium‐catalyzed asymmetric hydrogenation. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005  相似文献   

16.
A convenient and waste‐free synthesis of indene‐based tertiary carbinamines by rhodium‐catalyzed imine/alkyne [3+2] annulation is described. Under the optimized conditions of 0.5–2.5 mol % [{(cod)Rh(OH)}2] (cod=1,5‐cyclooctadiene) catalyst, 1,3‐bis(diphenylphosphanyl)propane (DPPP) ligand, in toluene at 120 °C, N‐unsubstituted aromatic ketimines and internal alkynes were coupled in a 1:1 ratio to form tertiary 1H‐inden‐1‐amines in good yields and with high selectivities over isoquinoline products. A plausible catalytic cycle involves sequential imine‐directed aromatic C? H bond activation, alkyne insertion, and a rare example of intramolecular ketimine insertion into a RhI–alkenyl linkage.  相似文献   

17.
Sterically similar palladium dicarbene complexes have been synthesized that comprise permethylated dicarbene ligands which bind the metal center either in a normal coordination mode via C2 or abnormally via C4. Due to the strong structural analogy of the complexes, differences in reactivity patterns may be attributed to the distinct electronic impact of normal versus abnormal carbene bonding, while stereoelectronic effects are negligible. Unique reactivity patterns have been identified for the abnormal carbene complexes, specifically upon reaction with Lewis acids and in oxidative addition‐reductive elimination sequences. These reactivities as well as analytical investigations using X‐ray diffraction and X‐ray photoelectron spectroscopy indicate that the C4 bonding mode increases the electron density at the metal center substantially, classifying such C4‐bound carbene ligands amongst the most basic neutral donors known thus far. A direct application of this enhanced electron density at the metal center is demonstrated by the catalytic H2 activation with abnormal carbene complexes under mild conditions, leading to a catalytic process for the hydrogenation of olefins.  相似文献   

18.
Methoxy‐substituted 1,6‐enynes react with arylboronic acids in the presence of a rhodium(I) complex to give arylated cyclization products. This occurs by a multi‐step mechanism consisting of rhodium/boron transmetalation, intermolecular carborhodation, intramolecular carborhodation, β‐hydride elimination, hydrorhodation, and β‐oxygen elimination. A shift of the position of a carbon–carbon double bond is observed, suggesting that the β‐hydride elimination/hydrorhodation process is repeatedly taking place.  相似文献   

19.
The oxidative olefination of sp2 C?H bonds of anilides with both activated and unactivated alkenes using an (electron‐deficient η5‐cyclopentadienyl)rhodium(III) complex is reported. In contrast to reactions using this electron‐deficient rhodium(III) catalyst, [Cp*RhCl2]2 showed no activity against olefination with unactivated alkenes. In addition, the deuterium kinetic isotope effect (DKIE) study revealed that the C?H bond cleavage step is thought to be the turnover‐limiting step.  相似文献   

20.
Various aryl‐, alkenyl‐, and/or alkyllithium species reacted smoothly with aryl and/or benzyl ethers with cleavage of the inert C?O bond to afford cross‐coupled products, catalyzed by commercially available [Ni(cod)2] (cod=1,5‐cyclooctadiene) catalysts with N‐heterocyclic carbene (NHC) ligands. Furthermore, the coupling reaction between the aryllithium compounds and aryl ammonium salts proceeded under mild conditions with C?N bond cleavage in the presence of a [Pd(PPh3)2Cl2] catalyst. These methods enable selective sequential functionalizations of arenes having both C?N and C?O bonds in one pot.  相似文献   

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