新型B(C6F5)3/有机胺盐酸盐催化体系的反应研究

近年来, 受限路易斯酸碱对(FLPs: Frustrated Lewis Pairs)在小分子的活化以及在催化还原等方面所表现出的独特反应特性, 使得有关FLPs化学的研究受到了国内外广泛的关注. 设计了一种新型的FLPs催化体系, 该体系以三(五氟苯基)硼(BCF)为路易斯酸, 以多种不同取代的有机胺盐酸盐替代常规FLPs中的路易斯碱有机胺. 发现利用该体系与氢化硅烷反应, 不仅可以高产率地制备分离得到相应的伯、仲、叔硼氢化胺盐; 而且还可以这一体系作为催化剂, 以氢化硅烷作为还原剂, 在常温常压下可高选择性地部分或彻底还原大部分含羰基官能团醛酮等有机化合物. 由BCF/2,2,6,6-四甲基哌啶(TMP)盐酸盐组成的催化体系在对CO₂催化还原为甲烷的反应中, 亦较相应的BCF/TMP体系显示更高的活性. 还通过核磁共振详细地对比研究了原料有机胺盐酸盐、中间体氯代硼胺盐以及产物氢化硼胺盐中, 胺基氮上质子的核磁共振谱信息, 发现不仅胺基上取代基的位阻效应会影响到具有电四极矩性的¹⁴N磁性核的弛豫效应, 而且阴离子基团的配位强弱对胺基氮上质子的化学位移也会产生较大的影响.     

One-pot B(C6F5)3 catalyzed cascade synthesis of 2-substituted-2,3-dihydroquinazolin-4(1H)-ones

Abstract

A new and efficient B(C₆F₅)₃ catalyzed domino strategy has been developed for the synthesis of 2-substituted quinazolinones. The reaction utilizes 2-aminobenzamide and aldehydes for a one-pot protocol. A wide range of substrate scope, functional group tolerance, and operational simplicity with excellent yield are synthetically useful features.     

Understanding the Influence of Donor-Acceptor Diazo Compounds on the Catalyst Efficiency of B(C6F5)3 Towards Carbene Formation

Diazo compounds have been largely used as carbene precursors for carbene transfer reactions in a variety of functionalization reactions. However, the ease of carbene generation from the corresponding diazo compounds depends upon the electron donating/withdrawing substituents either side of the diazo functionality. These groups strongly impact the ease of N₂ release. Recently, tris(pentafluorophenyl)borane [B(C₆F₅)₃] has been shown to be an alternative transition metal-free catalyst for carbene transfer reactions. Herein, a density functional theory (DFT) study on the generation of carbene species from α-aryl α-diazocarbonyl compounds using catalytic amounts of B(C₆F₅)₃ is reported. The significant finding is that the efficiency of the catalyst depends directly on the nature of the substituents on both the aryl ring and the carbonyl group of the substrate. In some cases, the boron catalyst has negligible effect on the ease of the carbene formation, while in other cases there is a dramatic reduction in the activation energy of the reaction. This direct dependence is not commonly observed in catalysis and this finding opens the way for intelligent design of this and other similar catalytic reactions.     

B(C6F5)3‐Catalyzed Hydrogenation of Oxime Ethers without Cleavage of the NO Bond

The hydrogenation of oximes and oxime ethers is usually hampered by N? O bond cleavage, hence affording amines rather than hydroxylamines. The boron Lewis acid B(C₆F₅)₃ is found to catalyze the chemoselective hydrogenation of oxime ethers at elevated or even room temperature under 100 bar dihydrogen pressure. The use of the triisopropylsilyl group as a protecting group allows for facile liberation of the free hydroxylamines.     

Pentafluorphenyliod(III)-Verbindungen. 2. Fluor-Aryl Substitution an Iodtrifluorid: Synthese von Pentafluorphenylioddifluorid C6F5IF2 und Bis(pentafluorphenyl)iodonium Pentafluorphenylfluoroboraten [(C6F5)2I]+[(C6F5)nBF4−n]−

Pentafluorophenyliodine(III) Compounds. 2. Fluorine-Aryl Substitution Reactions on Iodinetrifluoride: Synthesis of Pentafluorophenyliodinedifluoride C₆F₅IF₂ and Bis(pentafluorophenyl)iodonium Pentafluorophenylfluoroborates[(C₆F₅)₂I]⁺[(C₆F₅)_nBF_4?n]^? Mono- and disubstitution can be achieved in the fluorine-aryl substitution reaction on the low-temperature phase IF₃ in CH₂Cl₂ at ?78°C depending on the aryl transfer reagent. With B(C₆F₅)₃ [(C₆F₅)₂I]⁺ [(C₆F₅)_nBF_4?n]^? (68% yield) and with Cd(C₆F₅)₂ C₆F₅IF₂ (97% yield) is obtained whereas with C₆F₅SiMe₃ no fluorine-aryl substitution takes place on IF₃ even under basic conditions (EtCN or F^? addition). At ?78°C in EtCN solution IF₃ does not disproportionate but attacks the solvent under formation of HF.     

Methyl branching in polyethylene from homopolymerization of ethylene with N‐arylcyano‐β‐diketiminate methallyl nickel‐B(C6F5)3

N‐Arylcyano‐β‐diketiminate methallyl nickel complexes activated with B(C₆F₅)₃ were used in the polymerization of ethylene. The microstructure analysis of obtained polyethylene (PE) was done by differential scanning calorimetry and ¹³C nuclear magnetic resonance (NMR). The branched polymer structures produced by these catalysts were attributed to one step isomerization mechanism of the catalyst along the polymer chain. The ortho or para position of the cyano group with co‐ordinated B(C₆F₅)₃ in both methallyl nickel catalysts influenced the polymer molecular weight, branching, and consequently melting and crystallization temperatures. NMR spectroscopic studies showed predominantly the formation of methyl branches in the obtained PE. Catalysts under study gave linear low‐density PEs with good crystallinities at temperatures of reaction between 50 °C and 70 °C at moderate pressures (12.3 atm). A propylene–ethylene copolymer produced by the metallocene catalyst had the same concentration of branches as the PE synthesized from methallyl nickel/B(C₆F₅)₃. Comparing the two polyolefins with the same degree of branching, it was observed that the polymer obtained with the nickel catalyst proved to be twice more crystalline and had greater T_m. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 452–458     

Extending the Scope of the B(C6F5)3‐Catalyzed CN Bond Reduction: Hydrogenation of Oxime Ethers and Hydrazones

The B(C₆F₅)₃‐catalyzed hydrogenation is applied to aldoxime triisopropylsilyl ethers and hydrazones bearing an easily removable phthaloyl protective group. The C?N reduction of aldehyde‐derived substrates (oxime ethers and hydrazones) is enabled by using 1,4‐dioxane as the solvent known to participate as the Lewis‐basic component in FLP‐type heterolytic dihydrogen splitting. More basic ketone‐derived hydrazones act as Lewis bases themselves in the FLP‐type dihydrogen activation and are therefore successfully hydrogenated in nondonating toluene. The difference in reactivity between aldehyde‐ and ketone‐derived substrates is also reflected in the required catalyst loading and dihydrogen pressure.     

Adducts of (C6F5)3B with Selected Nitrogen

The Lewis acid (C₆F₅)₃B was reacted with ICN, NH₂CN, C₃N₃X₃ (X = H, Cl, F). The resulting Lewis acid base adducts ( 1—5 ) were fully characterized by analytic and spectroscopic methods. Additionally, the structures of the adducts 1—4 were determined by single crystal X‐ray analyses. It has been qualitatively shown, that a high field shift of the ¹¹B as well as the ¹⁹F NMR resonances of the o‐F atoms of the C₆F₅‐substituents suggests a longer B—N distance.     

B(C6F5)3 catalyzed synthesis of dihydropyrano[3,2-b]chromenediones under solvent-free conditions

Abstract

A simple, efficient, solventless, and one step, B(C₆F₅)₃ catalyzed, synthesis of dihydropyrano[3,2-b]chromenediones from dimedone, aldehyde and kojic acid is described. This protocol proceeds smoothly, accommodates aromatic as well as heteroaromatic aldehydes and gives dihydropyrano[3,2-b]chromenediones in excellent yield.     

Structures and Stability of Complexes of E(C6F5)3 (E = B,Al, Ga,In) with Acetonitrile

Complexes formed by interaction of E(C₆F₅)₃ (E = B, Al, Ga, In) with excess of acetonitrile (AN) were structurally characterized. Quantum chemical computations indicate that for Al(C₆F₅)₃ and In(C₆F₅)₃ the formation of a complex of 1:2 composition is more advantageous than for B(C₆F₅)₃ and Ga(C₆F₅)₃, in line with experimental observations. Formation of the solvate [Al(C₆F₅)₃ · 2AN] · AN is in agreement with predicted thermodynamic instability of [Al(C₆F₅)₃ · 3AN]. Tensimetry study of B(C₆F₅)₃ · CH₃CN reveals its stability in the solid state up to 197 °C. With the temperature increase, the complex undergoes irreversible thermal decomposition with pentafluorobenzene formation.     

B(C6F5)3‐Catalyzed Transfer Hydrogenation of Imines and Related Heteroarenes Using Cyclohexa‐1,4‐dienes as a Dihydrogen Source

The strong boron Lewis acid tris(pentafluorophenyl)borane, B(C₆F₅)₃, is shown to abstract a hydride from suitably donor‐substituted cyclohexa‐1,4‐dienes, eventually releasing dihydrogen. This process is coupled with the FLP‐type (FLP=frustrated Lewis pair) hydrogenation of imines and nitrogen‐containing heteroarenes that are catalyzed by the same Lewis acid. The net reaction is a B(C₆F₅)₃‐catalyzed, i.e., transition‐metal‐free, transfer hydrogenation using easy‐to‐access cyclohexa‐1,4‐dienes as reducing agents. Competing reaction pathways with or without the involvement of free dihydrogen are discussed.     

Boron Lewis Acid‐Catalyzed Hydroboration of Alkenes with Pinacolborane: BArF3 Does What B(C6F5)3 Cannot Do!

The transition‐metal‐free hydroboration of various alkenes with pinacolborane (HBpin) initiated by tris[3,5‐bis(trifluoromethyl)phenyl]borane (BAr^F₃) is reported. The choice of the boron Lewis acid is crucial as the more prominent boron Lewis acid tris(pentafluorophenyl)borane (B(C₆F₅)₃) is reluctant to react. Unlike B(C₆F₅)₃, BAr^F₃ is found to engage in substituent redistribution with HBpin, resulting in the formation of Ar^FBpin and the electron‐deficient diboranes [H₂BAr^F]₂ and [(Ar^F)(H)B(μ‐H)₂BAr^F₂]. These in situ‐generated hydroboranes undergo regioselective hydroboration of styrene derivatives as well as aliphatic alkenes with cis diastereoselectivity. Another ligand metathesis of these adducts with HBpin subsequently affords the corresponding HBpin‐derived anti‐Markovnikov adducts. The reactive hydroboranes are regenerated in this step, thereby closing the catalytic cycle.     

B(C6F5)3‐Catalyzed Tandem Friedel‐Crafts and C−H/C−O Coupling Reactions of Dialkylanilines

Tandem Friedel‐Crafts (FC) and C?H/C?O coupling reactions catalyzed by tris(pentafluorophenyl) borane (B(C₆F₅)₃) were achieved without using any other additive in the absence of solvent. This process can be used for the reactions between a series of dialkylanilines and vinyl ethers with good isolated yields of bis(4‐dialkylaminophenyl) compounds. Based on combined theoretical and experimental studies, the possible reaction mechanism was proposed. B(C₆F₅)₃ can activate the C=C and C?O bond for FC and C?H/C?O coupling reactions respectively. The FC reaction is slow, which is followed by a fast C?H/C?O coupling.     

B(C6F5)3-Catalyzed E-Selective Isomerization of Alkenes

Herein, we report the B(C₆F₅)₃-catalyzed E-selective isomerization of alkenes. The transition-metal-free method is applicable across a diverse array of readily accessible substrates, giving access to a broad range of synthetically useful products containing versatile stereodefined internal alkenes. The reaction mechanism was investigated by using synthetic and computational methods.     

B(C6F5)3-catalyzed synthesis of benzylic azides

B(C₆F₅)₃ was found to catalyze the reaction between trimethylsilyl azide and benzylic acetates. Secondary and tertiary benzylic acetates were competent substrates in this reaction providing the azide products in moderate to high yields. Mechanistic experiments are consistent with the possible formation of a Lewis acid-base pair between the B(C₆F₅)₃ and trimethylsilyl azide.     

Silver‐Catalyzed Oxidative C(sp3)−P Bond Formation through C−C and P−H Bond Cleavage

The silver‐catalyzed oxidative C(sp³)−H/P−H cross‐coupling of 1,3‐dicarbonyl compounds with H‐phosphonates, followed by a chemo‐ and regioselective C(sp³)−C(CO) bond‐cleavage step, provided heavily functionalized β‐ketophosphonates. This novel method based on a readily available reaction system exhibits wide scope, high functional‐group tolerance, and exclusive selectivity.     

The B(C6F5)3 Boron Lewis Acid Route to Arene‐Annulated Pentalenes

4,5‐Dimethyl‐1,2‐bis(1‐naphthylethynyl)benzene ( 12 ) undergoes a rapid multiple ring‐closure reaction upon treatment with the strong boron Lewis acid B(C₆F₅)₃ to yield the multiply annulated, planar conjugated π‐system 13 (50 % yield). In the course of this reaction, a C₆F₅ group was transferred from boron to carbon. Treatment of 12 with CH₃B(C₆F₅)₂ proceeded similarly, giving a mixture of 13 (C₆F₅‐transfer) and the product 15 , which was formed by CH₃‐group transfer. 1,2‐Bis(phenylethynyl)benzene ( 8 a ) reacts similarly with CH₃B(C₆F₅)₂ to yield a mixture of the respective C₆F₅‐ and CH₃‐substituted dibenzopentalenes 10 a and 16 . The reaction is thought to proceed through zwitterionic intermediates that exhibit vinyl cation reactivities. Some B(C₆F₅)₃‐substituted species ( 26 , 27 ) consequently formed by in situ deprotonation upon treatment of the respective 1,2‐bis(alkynyl)benzene starting materials ( 24 , 8 ) with the frustrated Lewis pair B(C₆F₅)₃/P(o‐tolyl)₃. The overall formation of the C₆F₅‐substituted products formally require HB(C₆F₅)₂ cleavage in an intermediate dehydroboration step. This was confirmed in the reaction of a thienylethynyl‐containing starting material 21 with B(C₆F₅)₃, which gave the respective annulated pentalene product 23 that had the HB(C₆F₅)₂ moiety 1,4‐added to its thiophene ring. Compounds 12 – 14 , 23 , and 26 were characterized by X‐ray diffraction.