A Cobalt‐Catalyzed Alkene Hydroboration with Pinacolborane

An extremely efficient cobalt catalyst for the hydroboration of both vinylarenes and aliphatic α‐olefins with pinacolborane is described, providing the anti‐Markovnikov products with excellent regio‐ and chemoselectivity, broad functional‐group tolerance, and high turnover numbers (up to 19 800). The alkene hydroboration route is further extended to a two‐step, one‐pot hydroboration and cross‐coupling of alkylboronates with aryl chlorides.     

Magnesium Catalysis of Imine Hydroboration

The β‐diketiminato magnesium alkyl complex [LMgnBu] (L=CH{CMe(NDipp)}₂, Dipp=diisopropylphenyl) is shown to be a highly effective precatalyst for the hydroboration of alkyl and aryl substituted aldimines and ketimines with pinacol borane (HBpin). Catalysis is proposed to occur through a sequence of Mg? N/B? H metathesis and rate‐determining Mg? H/N?C insertion steps, a proposal strongly supported by stoichiometric studies and kinetic analysis. The reactions are observed to proceed through the intermediacy of well‐defined magnesium amides, two examples of which have been isolated and structurally characterized. Mechanistic investigations suggest that the catalytic rate‐determining process occurs at an isolated magnesium center and requires the presence of two molecules of the imine substrate for effective turnover. This latter observation is rationalized as a requirement for the secondary substrate molecule to displace HBpin from the coordination sphere of the catalytic magnesium center.     

Magnesium Catalysis for the Hydroboration of Carbodiimides

A β‐diketiminato magnesium alkyl complex, [CH{C(Me)NDipp}₂}MgnBu] (Dipp=2,6‐iPr₂C₆H₃), was shown to be an effective pre‐catalyst for the first reported catalytic hydroboration of alkyl‐ and aryl‐substituted carbodiimides with pinacol borane (HBpin). The catalytic reactions proceed under mild conditions to afford the corresponding N‐borylated formamidine compounds in good yields. The reactions were observed to proceed through the intermediacy of magnesium amidinate and formamidinatoborate intermediates and an example of one of these latter species has been structurally characterised by an X‐ray diffraction analysis. Crucially, no formation of the N‐boryl formamidine products was observed in the absence of additional equivalents of the carbodiimide and HBpin substrates. This observation, supported by the evolution of a sigmoidal kinetic profile for the hydroboration of dicyclohexylcarbodiimide, has been rationalised as the consequence of an allosteric effect of the pinacol borane and carbodiimide on the magnesium formamidinatoborate intermediates.     

Ligand‐Controlled Regiodivergent Enantioselective Rhodium‐Catalyzed Alkene Hydroboration

Regiocontrol in the rhodium‐catalyzed boration of vinyl arenes is typically dominated by the presence of the conjugated aryl substituent. However, small differences in TADDOL‐derived chiral monophosphite ligands can override this effect and direct rhodium‐catalyzed hydroboration of β‐aryl and β‐heteroaryl methylidenes by pinacolborane to selectively produce either chiral primary or tertiary borated products. The regiodivergent behavior is coupled with enantiodivergent addition of the borane. The nature of the TADDOL backbone substituents and that of the phosphite moiety function synergistically to direct the sense and extent of regioselectivity and enantioinduction. Twenty substrates are shown to undergo each reaction mode with regioselectivity values reaching greater than 20:1 and enantiomer ratios reaching up to 98:2. A variety of subsequent transformations illustrate the potential utility of each product.     

Crystal Structures of Two Monomeric Copper(II) Carboxylates with 2-Aminopyridine

The crystal structures of two monomeric copper(II) carboxylates with 2-aminopyridine have been determined by X-ray diffraction. The hexanoate complex crystallizes as its acetonitrile solvate [Cu(C₆H₁₁O₂)₂(C₅H₆N₂)₂ · CH₃CN] in the triclinic space group P-1 with a = 8.1020(6), b = 13.7106(9), c = 13.7673(9) Å, = 113.79(1), = 103.86(1), and = 94.38(4). The heptanoate compound shows an unsolvated structure [Cu(C₇H₁₃O₂)₂(C₅H₆N₂)₂] and also crystallizes in the triclinic space group P-1 with the following cell parameters: a = 8.4487(9), b = 12.238(1), c = 13.504(2) Å, = 87.034(9), = 77.489(9), and = 71.41(1)^°. Both compounds contain the CuO₄N₂ chromophore, with ligands arranged around the copper center in a cis mode. 2-Aminopyridine is coordinated through the endocyclic nitrogen atom. The ortho position of the amino group, with respect to the pyridine nitrogen atom, allows the formation of both, intra-and intermolecular hydrogen bonds.     

Cobalt‐Catalyzed Alkyne Hydrosilylation and Sequential Vinylsilane Hydroboration with Markovnikov Selectivity

A pyridinebis(oxazoline) cobalt complex is a very efficient precatalyst for the hydrosilylation of terminal alkynes with Ph₂SiH₂, providing α‐vinylsilanes with high (Markovnikov) regioselectivity and broad functional‐group tolerance. The vinylsilane products can be further converted into geminal borosilanes through Markovnikov hydroboration with pinacolborane and a bis(imino)pyridine cobalt catalyst.     

Alkene and Alkyne Oxidative Cleavage Catalyzed by RuO4 in Environmentally Acceptable Solvents

Abstract

The application of CCl₄, C₆H₁₂, EtOAc, and Me₂CO as solvents for biphasic systems has been compared for oxidative cleavage of alkenes and alkynes by RuO₄ to carboxylic acids, using the RuCl₃ · nH₂O–IO(OH)₅ reagent for which an improved procedure is described. Cyclohexane is an effective and economic replacement for the environmentally unfriendly CCl₄; acetone and ethyl acetate are less effective.     

Traceless Chelation‐Controlled Rhodium‐Catalyzed Intermolecular Alkene and Alkyne Hydroacylation

A new functional‐group tolerant, rhodium‐catalyzed, sulfide‐reduction process is combined with rhodium‐catalyzed chelation‐controlled hydroacylation reactions to give a traceless hydroacylation protocol. Aryl‐ and alkenyl aldehydes can be combined with both alkenes, alkynes and allenes to give traceless products in high yields. A preliminary mechanistic proposal is also presented.     

磷酸铵镁法回收稀土分离废水中镁及氨氮的研究

磷酸铵镁法是一种有效的回收氨氮、磷和镁的方法。本文通过热力学计算,分析了反应过程及pH值对磷酸铵镁生成的影响规律。根据理论分析结果,进行了pH值、磷源、加料方式等因素对氨氮、磷去除率的影响实验。结果表明:以Na3PO4为磷源,通过向氮磷混合液中加入含镁废水,并控制反应液pH值为9时,氮磷镁去除率均可达98%以上,得到沉淀物经X衍射分析为六水磷酸铵镁。     

(N‐Phosphinoamidinate)cobalt‐Catalyzed Hydroboration: Alkene Isomerization Affords Terminal Selectivity

Herein we establish the utility of a three‐coordinate (N‐phosphinoamidinate)cobalt(amido) pre‐catalyst that is capable of effecting challenging alkene isomerization/hydroboration processes at room temperature, leading to the selective terminal addition of the boron group.     

Discrete Cationic Zinc and Magnesium Complexes for Dual Organic/Organometallic‐Catalyzed Ring‐Opening Polymerization of Trimethylene Carbonate

We describe herein an original approach for the efficient immortal ring‐opening polymerization (iROP) of trimethylene carbonate (TMC) under mild conditions using dual‐catalyst systems combining a discrete cationic metal complex with a tertiary amine. A series of new zinc and magnesium cationic complexes of the type [{NNO}M]⁺[anion]^? ({NNO}^?=2,4‐di‐tert‐butyl‐6‐{[(2′‐dimethylaminoethyl)methylamino]methyl}phenolate; M=Zn, [anion]^?=[B(C₆F₅)₄]^? ( 2 ), [H₂N‐ {B(C₆F₅)₃}₂]^? ( 3 ), and [EtB(C₆F₅)₃]^? ( 4 ); M=Mg, [anion]^?=[H₂N{B(C₆F₅)₃}₂]^? ( 7 )) have been prepared from the corresponding neutral compounds [{NNO}ZnEt] ( 1 ) and [{NNO}‐ Mg(nBu)] ( 6 ). Compounds 2 – 4 and 7 exist as free ion pairs, as revealed by ¹H, ¹³C, ¹⁹F, and ¹¹B NMR spectroscopy in THF solution, and an X‐ray crystallographic analysis of the bis(THF) adduct of compound 7 , 7? (THF)₂. The neutral complexes 1 and 6 , in combination with one equivalent or an excess of benzyl alcohol (BnOH), initiate the rapid iROP of TMC, in bulk or in toluene solution, at 45–60 °C (turnover frequency, TOF, up to 25–30 000 mol(TMC)?mol(Zn)?h^?1 for 1 and 220–240 000 mol(TMC)?mol(Mg)?h^?1 for 6 ), to afford H‐PTMC‐OBn with controlled macromolecular features. ROP reactions mediated by the cationic systems 2 /BnOH and 7 /BnOH proceeded much more slowly (TOF up to 500 and 3 000 mol(TMC)?mol(Zn or Mg)?h^?1 at 110 °C) than those based on the parent neutral compounds 1 /BnOH and 6 /BnOH, respectively. Use of original dual organic/organometallic catalyst systems, obtained by adding 0.2–5 equiv of a tertiary amine such as NEt₃ to zinc cationic complexes [{NNO}Zn]⁺[anion]^? ( 2 – 4 ), promoted high activities (TOF up to 18 300 mol(TMC)?mol(Zn)?h^?1 at 45 °C) giving H‐PTMC‐OBn with good control over the M_n and M_w/M_n values. Variation of the nature of the anion in 2 – 4 did not significantly affect the performance of these catalyst systems. On the other hand, the dual magnesium‐based catalyst system 7 /NEt₃ proved to be poorly effective.     

Synthesis of Cyclic Amine Boranes through Triazole‐Gold(I)‐Catalyzed Alkyne Hydroboration

The first catalytic alkyne hydroboration of propargyl amine boranecarbonitriles is accomplished with triazole‐Au^I complexes. While the typical [L‐Au]⁺ species decomposes within minutes upon addition of amine boranecarbonitriles, the triazole‐modified gold catalysts (TA‐Au) remained active, and allowed the synthesis of 1,2‐BN‐cyclopentenes in one step with good to excellent yields. With good substrate tolerability and mild reaction conditions (open‐flask), this new method provides an alternative route to reach the interesting cyclic amine borane with high efficiency.     

Reaching Milestones in the Oxygenation Chemistry of Magnesium Alkyls: towards Intimate States of O2 Activation and the First Monomeric Well-Defined Magnesium Alkylperoxide

Despite decades of extensive studies on the reactivity of magnesium alkyls towards O₂, the isolation and structural characterization of discrete products of these reactions still remains a challenge. Although the formation of the most frequently encountered magnesium alkoxides through unstable alkylperoxide intermediates has commonly been accepted, the latter species have been elusive for over 100 years. Probing the oxygenation of a seemingly simple well-defined neo-pentylmagnesium complex stabilized by a β-diketiminate ligand, (^dippBDI)MgCH₂CMe₃, we report on the isolation and structure characterization of both a dimeric magnesium alkoxide [(^dippBDI)Mg(μ-OCH₂CMe₃)]₂ and the first example of monomeric magnesium alkylperoxide [(^dippBDI)Mg(thf)OOCH₂CMe₃] (^dippBDI=[(ArNCMe)₂CH]⁻ and Ar=C₆H₃iPr₂-2,6). The formation of monomeric magnesium alkylperoxide demonstrates a crucial role of an additional Lewis base for stabilizing the most elusive oxygenation products likely due to increasing of the electron density on the metal centre. Moreover, the ¹H NMR studies at −80 °C revealed that the dissociation of a coordinated Lewis base from the solvated complex (^dippBDI)Mg(L)CH₂CMe₃ (where L=thf or 4-methylpyridine) is likely not required prior to the effective attack of an O₂ molecule on the metal centre and the four-coordinate alkylmagnesium complex reacts smoothly with O₂ under these conditions. The results can be expected to aid future engineering of various organomagnesium/O₂-based reaction systems.     

Synthesis of a Hexameric Magnesium 4-pyridyl Complex with Cyclohexane-like Ring Structure via Reductive C-N Activation

The reaction of [{(^Arnacnac)Mg}₂] (^Arnacnac = HC{MeC(NAr)}₂, Ar = 2,6-diisopropylphenyl, Dip, or 2,6-diethylphenyl, Dep) with 4-dimethylaminopyridine (DMAP) at elevated temperatures afforded the hexameric magnesium 4-pyridyl complex [{(^Arnacnac)Mg(4-C₅H₄N)}₆] via reductive cleavage of the DMAP C-N bond. The title compound contains a large s-block organometallic cyclohexane-like ring structure comprising tetrahedral (^Arnacnac)Mg nodes and linked by linear 4-pyridyl bridging ligands, and the structure is compared with other ring systems. [(^Dipnacnac)Mg(DMAP)(NMe₂)] was structurally characterised as a by-product.     

Cyanosilylation of Aldehydes and Ketones Catalyzed by Nanocrystalline Magnesium Oxide

Abstract

Cyanosilylation of various aldehydes and ketones with TMSCN proceeded smoothly under mild conditions to give the corresponding cyanohydrin trimethylsilyl ethers in the presence of nanocrystalline magnesium oxide. The cyanohydrin trimethylsilyl ethers of aldehydes produced cyanohydrins in good to high yields on treatment with 2 N HCl. ²⁹Si NMR spectral evidence proved that the reaction proceeds through the hypervalent silicate species by coordination to O^2?/O^? (Lewis basic site) of nanocrystalline magnesium oxide.     

Hydroxy‐Directed Ruthenium‐Catalyzed Alkene/Alkyne Coupling: Increased Scope,Stereochemical Implications,and Mechanistic Rationale

The recognition of the dual binding mode of propargyl and allyl alcohols to [Cp*Ru] fragments fostered the development of a highly regioselective intermolecular Alder‐ene‐type reaction of alkynes with 1,2‐disubstituted alkenes. The increased substrate scope opens new perspectives in stereochemical terms. As the loaded catalyst is chiral‐at‐metal, stereochemical information is efficiently relayed from the propargylic site to the emerging C−C bond. This interpretation is based on the X‐ray structure of the first Cp*Ru complex carrying an intact enyne ligand, and provides valuable insights into bonding and activation of the substrates. Computational data draw a clear picture of the principles governing regio‐ and stereocontrol.