Stable Mesoionic N-Heterocyclic Olefins (mNHOs)

We report a new class of stable mesoionic N-heterocyclic olefins, featuring a highly polarized (strongly ylidic) double bond. The ground-state structure cannot be described through an uncharged mesomeric Lewis-structure, thereby structurally distinguishing them from traditional N-heterocyclic olefins (NHOs). mNHOs can easily be obtained through deprotonation of the corresponding methylated N,N′-diaryl-1,2,3-triazolium and N,N′-diaryl-imidazolium salts, respectively. In their reactivity, they represent strong σ-donor ligands as shown by their coordination complexes of rhodium and boron. Their calculated proton affinities, their experimentally derived basicities (competition experiments), as well as donor abilities (Tolman electronic parameter; TEP) exceed the so far reported class of NHOs.     

N‐Heterocyclic Olefins as Organocatalysts for Polymerization: Preparation of Well‐Defined Poly(propylene oxide)

The metal‐free polymerization of propylene oxide (PO) using a special class of alkene—N‐heterocyclic olefins (NHOs)—as catalysts is described. Manipulation of the chemical structure of the NHO organocatalyst allows for the preparation of the poly(propylene oxide) in high yields with high turnover (TON>2000), which renders this the most active metal‐free system for the polymerization of PO reported to date. The resulting polyether displays predictable end groups, molar mass, and a low dispersity (?_M<1.09). NHOs with an unsaturated backbone are essential for polymerization to occur, while substitution at the exocyclic carbon atom has an impact on the reaction pathway and ensures the suppression of side reactions.     

Access to Pyrazolidin‐3,5‐diones through Anodic N–N Bond Formation

Pyrazolidin‐3,5‐diones are important motifs in heterocyclic chemistry and are of high interest for pharmaceutical applications. In classic organic synthesis, the hydrazinic moiety is installed through condensation using the corresponding hydrazine building blocks. However, most N,N′‐diaryl hydrazines are toxic and require upstream preparation owing to their low commercial availability. We present an alternative and sustainable synthetic approach to pyrazolidin‐3,5‐diones that employs readily accessible dianilides as precursors, which are anodically converted to furnish the N?N bond. The electroconversion is conducted in a simple undivided cell under constant‐current conditions.     

Selective Activation of Fluoroalkenes with N‐Heterocyclic Carbenes: Synthesis of N‐Heterocyclic Fluoroalkenes and Polyfluoroalkenyl Imidazolium Salts

Selective reactions between nucleophilic N,N′‐diaryl‐heterocyclic carbenes (NHCs) and electrophilic fluorinated alkenes afford NHC fluoroalkenes in high yields. These stable compounds undergo efficient and selective fluoride abstraction with Lewis acids to give polyfluoroalkenyl imidazolium salts. These salts react at Cβ with pyrrolidine to give ammonium fluoride‐substituted salts, which give rise to conjugated imidazolium‐enamine salts through loss of HF. Alternatively, reaction with 4‐(dimethylamino)‐pyridine provides a Cα‐pyridinium‐substituted NHC fluoroalkene. These compounds were studied using multinuclear NMR spectroscopy, mass spectrometry, and X‐ray crystallography. Insight into their electronic structure and reactivity was gained through the use of DFT calculations.     

Chemoselectivity in the Reaction of 2‐Diazo‐3‐oxo‐3‐phenylpropanal with Aldehydes and Ketones

The chemoselectivity in the reaction of 2‐diazo‐3‐oxo‐3‐phenylpropanal ( 1 ) with aldehydes and ketones in the presence of Et₃N was investigated. The results indicate that 1 reacts with aromatic aldehydes with weak electron‐donating substituents and cyclic ketones under formation of 6‐phenyl‐4H‐1,3‐dioxin‐4‐one derivatives. However, it reacts with aromatic aldehydes with electron‐withdrawing substituents to yield 1,3‐diaryl‐3‐hydroxypropan‐1‐ones, accompanied by chalcone derivatives in some cases. It did not react with linear ketones, aliphatic aldehydes, and aromatic aldehydes with strong electron‐donating substituents. A mechanism for the formation of 1,3‐diaryl‐3‐hydroxypropan‐1‐ones and chalcone derivatives is proposed. We also tried to react 1 with other unsaturated compounds, including various olefins and nitriles, and cumulated unsaturated compounds, such as N,N′‐dialkylcarbodiimines, phenyl isocyanate, isothiocyanate, and CS₂. Only with N,N′‐dialkylcarbodiimines, the expected cycloaddition took place.     

Consecutive Intermolecular Reductive Amination/Asymmetric Hydrogenation: Facile Access to Sterically Tunable Chiral Vicinal Diamines and N‐Heterocyclic Carbenes

A highly enantioselective iridium‐ or ruthenium‐catalyzed intermolecular reductive amination/asymmetric hydrogenation relay with 2‐quinoline aldehydes and aromatic amines has been developed. A broad range of sterically tunable chiral N,N′‐diaryl vicinal diamines were obtained in high yields (up to 95 %) with excellent enantioselectivity (up to >99 % ee). The resulting chiral diamines could be readily transformed into sterically hindered chiral N‐heterocyclic carbene (NHC) precursors, which are otherwise difficult to access. The usefulness of this synthetic approach was further demonstrated by the successful application of one of the chiral vicinal diamines and chiral NHC ligands in a transition‐metal‐catalyzed asymmetric Suzuki–Miyaura cross‐coupling reaction and asymmetric ring‐opening cross‐metathesis, respectively.     

N-Heterocyclic Olefin-Ligated Palladium(II) Complexes as Pre-Catalysts for Buchwald–Hartwig Aminations

New N-heterocyclic olefins (NHOs) are described with functionalization on the ligand heterocyclic backbone and terminal alkylidene positions. Various Pd^II–NHO complexes have been formed and their use as pre-catalysts in Buchwald–Hartwig aminations was explored. The most active system for catalytic C−N bond formation between hindered arylamine and arylhalide substrates was accessed by combining a backbone methylated NHO with [Pd(cinnamyl)Cl]₂ in the presence of NaOtBu as a base. In these active systems evidence suggests that catalysis is mediated by colloidal palladium metal, highlighting a different coordination ability of NHOs in comparison with commonly used N-heterocyclic carbene co-ligands.     

Donor‐Flexible Bis(pyridylidene amide) Ligands for Highly Efficient Ruthenium‐Catalyzed Olefin Oxidation

An exceptionally efficient ruthenium‐based catalyst for olefin oxidation has been designed by exploiting N,N′‐bis(pyridylidene)oxalamide (bisPYA) as a donor‐flexible ligand. The dynamic donor ability of the bisPYA ligand, imparted by variable zwitterionic and neutral resonance structure contributions, paired with the redox activity of ruthenium provided catalytic activity for Lemieux–Johnson‐type oxidative cleavage of olefins to efficiently prepare ketones and aldehydes. The ruthenium bisPYA complex significantly outperforms state‐of‐the‐art systems and displays extraordinary catalytic activity in this oxidation, reaching turnover frequencies of 650 000 h^?1 and turnover numbers of several millions.     

Structural Diversity in Alkali Metal and Alkali Metal Magnesiate Chemistry of the Bulky 2,6‐Diisopropyl‐N‐(trimethylsilyl)anilino Ligand

Bulky amido ligands are precious in s‐block chemistry, since they can implant complementary strong basic and weak nucleophilic properties within compounds. Recent work has shown the pivotal importance of the base structure with enhancement of basicity and extraordinary regioselectivities possible for cyclic alkali metal magnesiates containing mixed n‐butyl/amido ligand sets. This work advances alkali metal and alkali metal magnesiate chemistry of the bulky arylsilyl amido ligand [N(SiMe₃)(Dipp)]^? (Dipp=2,6‐iPr₂‐C₆H₃). Infinite chain structures of the parent sodium and potassium amides are disclosed, adding to the few known crystallographically characterised unsolvated s‐block metal amides. Solvation by N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine (PMDETA) or N,N,N′,N′‐tetramethylethylenediamine (TMEDA) gives molecular variants of the lithium and sodium amides; whereas for potassium, PMDETA gives a molecular structure, TMEDA affords a novel, hemi‐solvated infinite chain. Crystal structures of the first magnesiate examples of this amide in [MMg{N(SiMe₃)(Dipp)}₂(μ‐nBu)]_∞ (M=Na or K) are also revealed, though these breakdown to their homometallic components in donor solvents as revealed through NMR and DOSY studies.     

Synthesis of 1,3‐Selenazol‐2(3H)‐imines

The reaction of N,N′‐diarylselenoureas 16 with phenacyl bromide in EtOH under reflux, followed by treatment with NH₃, gave N,3‐diaryl‐4‐phenyl‐1,3‐selenazol‐2(3H)‐imines 13 in high yields (Scheme 2). A reaction mechanism via formation of the corresponding Se‐(benzoylmethyl)isoselenoureas 18 and subsequent cyclocondensation is proposed (Scheme 3). The N,N′‐diarylselenoureas 16 were conveniently prepared by the reaction of aryl isoselenocyanates 15 with 4‐substituted anilines. The structures of 13a and 13c were established by X‐ray crystallography.     

Large yet Flexible N‐Heterocyclic Carbene Ligands for Palladium Catalysis

A straightforward and scalable eight‐step synthesis of new N‐heterocyclic carbenes (NHCs) has been developed from inexpensive and readily available 2‐nitro‐m‐xylene. This process allows for the preparation of a novel class of NHCs coined ITent (“Tent” for “tentacular”) of which the well‐known IMes (N,N′‐bis(2,4,6‐trimethylphenyl)imidazol‐2‐ylidene), IPr (N,N′‐bis(2,6‐di(2‐propyl)phenyl)imidazol‐2‐ylidene) and IPent (N,N′‐bis(2,6‐di(3‐pentyl)phenyl)imidazol‐2‐ylidene) NHCs are the simplest and already known congeners. The synthetic route was successfully used for the preparation of three members of the ITent family: IPent (N,N′‐bis(2,6‐di(3‐pentyl)phenyl)imidazol‐2‐ylidene), IHept (N,N′‐bis(2,6‐di(4‐heptyl)phenyl)imidazol‐2‐ylidene) and INon (N,N′‐bis(2,6‐di(5‐nonyl)phenyl)imidazol‐2‐ylidene). The electronic and steric properties of each NHC were studied through the preparation of both nickel and palladium complexes. Finally the effect of these new ITent ligands in Pd‐catalyzed Suzuki–Miyaura and Buchwald–Hartwig cross‐couplings was investigated.     

Lewis Pair Polymerization of Epoxides via Zwitterionic Species as a Route to High‐Molar‐Mass Polyethers

A dual catalytic setup based on N‐heterocyclic olefins (NHOs) and magnesium bis(hexamethyldisilazide) (Mg(HMDS)₂) was used to prepare poly(propylene oxide) with a molar mass (M_n) >500 000 g mol^?1, in some cases even >10⁶ g mol^?1, as determined by GPC/light scattering. This is achieved by combining the rapid polymerization characteristics of a zwitterionic, Lewis pair type mechanism with the efficient epoxide activation by the Mg^II species. Transfer‐to‐monomer, traditionally frustrating attempts at synthesizing polyethers with a high degree of polymerization, is practically removed as a limiting factor by this approach. NMR and MALDI‐ToF MS experiments reveal key aspects of the proposed mechanism, whereby the polymerization is initiated via nucleophilic attack by the NHO on the activated monomer, generating a zwitterionic species. This strategy can also be extended to other epoxides, including functionalized monomers.     

Novel regioselective synthesis of 3′H,4H‐spiro[chromene‐3,2′‐[1,3,4]thiadiazol]‐4‐one containing compounds

A variety of 3″,5″‐diaryl‐3″H,4′H‐dispiro[cyclohexane‐1,2′‐chromene‐3′,2″‐[1,3,4]thiadiazol]‐4′‐ones 3a‐c were synthesized regioselectively through the reaction of 4′H,5H‐trispiro[cyclohexane‐1,2′‐chromene‐3′,2″‐[1,3,4]oxadithiino[5,6‐c]chromene‐5″,1″′‐cyclohexan]‐4′‐one ( 1 ) with nitrilimines (generated in situ via triethylamine dehydrohalogenation of the corresponding hydrazonoyl chlorides 2a‐c ) in refluxing dry toluene. Single crystal X‐ray diffraction studies of 3a,b add support for the established structure. Similarly, 3′,5′‐diaryl‐2,2‐dimethyl‐3′H,4H‐spiro[chromene‐3,2′‐[1,3,4]thiadiazol]‐4‐ones 5a‐c were obtained in a regioselective manner through the reaction of 2,2,5′,5′‐tetramethyl‐4H,5′H‐spiro[chromene‐3,2′‐[1,3,4]oxadithiino[5,6‐c]chromen]‐4‐one ( 4a ) with nitrilimines under similar reaction conditions. On the other hand, reaction of 2,5′‐diethyl‐2,5′‐dimethyl‐4H,5′H‐spiro[chromene‐3,2′‐[1,3,4]oxadithiino‐[5,6‐c]chromen]‐4‐one ( 4b ) with nitrilimines in refluxing dry toluene afforded the corresponding 3′,5′‐diaryl‐2‐ethyl‐2‐methyl‐3′H,4H‐spiro[chromene‐3,2′‐[1,3,4]thiadiazol]‐4‐ones 5d‐f as two unisolable diastereoisomeric forms.     

Nucleosides XII.1 Synthesis of 5‐Modified Isoguanosines and Reinvestigation of 5′‐Deoxy‐N3,5′‐cycloisoguanosine

Isoguanosine ( 3 ) underwent a coupling reaction with diaryl disulfides in the presence of tri‐n‐butylphosphine when its 6‐amino group was protected by N,N‐dimethylaminomethylidene. The synthesis of 5′‐deoxy‐N³,5′‐cycloisoguanosine ( 6 ) and its 2′,3′‐O‐isopropylidene derivative ( 11 ) were accomplished in excellent yields from isoguanosines ( 3 & 10 ) in the presence of triphenylphospine and carbon tetrachloride in pyridine. Chlorination at the 5′‐position of isoguanosine ( 3 ) with thionyl chloride followed by the aqueous base‐promoted cyclization afforded the same product 6 . The structures were elucidated by spectroscopic analysis including IR, UV, 1‐D and 2‐D NMR.     

2′‐Deoxy‐7‐propynyl‐7‐deaza­adenosine: a DNA duplex‐stabilizing nucleoside

In the title compound, 2′‐deoxy‐7‐propynyl‐7‐deaza­adenosine, C₁₄H₁₆N₄O₃, the torsion angle of the N‐glycosylic bond is anti [χ = −130.7 (2)°]. The sugar pucker of the 2′‐deoxy­ribo­furanosyl moiety is C2′‐endo–C3′‐exo, ²T₃ (S‐type), with P = 185.9 (2)° and τ_m = 39.1 (1)°, and the orientation of the exocyclic C4′—C5′ bond is −ap (trans). The 7‐substituted propynyl group is nearly coplanar with the heterocyclic base moiety. Mol­ecules of the nucleoside form a layered network in which the heterocyclic bases are stacked head‐to‐tail with a closest distance of 3.197 (1) Å. The crystal structure of the nucleoside is stabilized by three inter­molecular hydrogen bonds of types N—H⋯ O, O—H⋯ N and O—H⋯ O.     

Deep Red to Near‐Infrared Emitting Rhenium(I) Complexes: Synthesis,Characterization, Electrochemistry,Photophysics, and Electroluminescence Studies

A series of triarylamine‐containing tricarbonyl rhenium(I) complexes, [BrRe(CO)₃(N^N)] (N^N=5,5′‐bis(N,N‐diaryl‐4‐[ethen‐1‐yl]‐aniline)‐2,2′‐bipyridine), has been designed and synthesized by introducing a rhenium(I) metal center into a donor‐π‐acceptor‐π‐donor structure. All of the complexes showed an intense broad structureless emission band in dichloromethane at around 680–708 nm, which originated from an excited state of intraligand charge transfer (³ILCT) character from the triarylamine to the bipyridine moiety. Upon introduction of the bulky and electron‐donating pentaphenylbenzene units attached to the aniline groups, the emission bands were found to be red shifted. The nanosecond transient absorption spectra of two selected complexes were studied, which were suggestive of the formation of an initial charge‐separated state. Computational studies have been performed to provide further insight into the origin of the absorption and emission. One of the rhenium(I) complexes has been utilized in the fabrication of organic light‐emitting diodes (OLEDs), representing the first example of the realization of deep red to near‐infrared rhenium(I)‐based OLEDs with an emission extending up to 800 nm.     

Novel (N‐heterocyclic carbene)Pd(pyridine)Br2 complexes for carbonylative Sonogashira coupling reactions: Catalytic efficiency and scope for arylalkynes,alkylalkynes and dialkynes

New N,N′‐substituted imidazolium salts and their corresponding dibromidopyridine–palladium(II) complexes were successfully synthesized and characterized. Reactions of palladium bromide with the newly synthesized N,N′‐substituted imidazolium bromides ( 2a and 2b ) in pyridine afforded the corresponding new N‐heterocyclic carbene pyridine palladium(II) complexes ( 3a and 3b ) in high yields. Their single‐crystal X‐ray structures show a distorted square planar geometry with the carbene and pyridine ligands in trans position. Both complexes show a high catalytic activity in carbonylative Sonogashira coupling reactions of aryl iodides and aryl diiodides with arylalkynes, alkylalkynes and dialkynes.     

Structure and spectroscopic properties of the dimeric copper(I) N‐heterocyclic carbene complex [Cu2(CNCt‐Bu)2](PF6)2

In recent years, the use of copper N‐heterocyclic carbene (NHC) complexes has expanded to fields besides catalysis, namely medicinal chemistry and luminescence applications. In the latter case, multinuclear copper NHC compounds have attracted interest, however, the number of these complexes in the literature is still quite limited. Bis[μ‐1,3‐bis(3‐tert‐butylimidazolin‐2‐yliden‐1‐yl)pyridine]‐1κ⁴C²,N:N,C^2′;2κ⁴C²,N:N,C^2′‐dicopper(I) bis(hexafluoridophosphate), [Cu₂(C₁₉H₂₅N₅)₂](PF₆)₂, is a dimeric copper(I) complex bridged by two CNC, i.e. bis(N‐heterocyclic carbene)pyridine, ligands. Each Cu^I atom is almost linearly coordinated by two NHC ligands and interactions are observed between the pyridine N atoms and the metal centres, while no cuprophilic interactions were observed. Very strong absorption bands are evident in the UV–Vis spectrum at 236 and 274 nm, and an emission band is observed at 450 nm. The reported complex is a new example of a multinuclear copper NHC complex and a member of a compound class which has only rarely been reported.     

The heterobifunctional ligand 5‐[4‐(1,2,4‐triazol‐4‐yl)phenyl]‐1H‐tetrazole and its role in the construction of a CdII metal–organic chain structure

5‐[4‐(1,2,4‐Triazol‐4‐yl)phenyl]‐1H‐tetrazole, C₉H₇N₇, (I), an asymmetric heterobifunctional organic ligand containing triazole (tr) and tetrazole (tz) termini linked directly through a 1,4‐phenylene spacer, crystallizes in the polar space group Pc. The heterocyclic functions, serving as single hydrogen‐bond donor (tz) or acceptor (tr) units, afford hydrogen‐bonded zigzag chains with no crystallographic centre of inversion. In the structure of catena‐poly[[diaquacadmium(II)]bis{μ₂‐5‐[4‐(1,2,4‐triazol‐4‐yl)phenyl]tetrazol‐1‐ido‐κ²N¹:N^1′}], [Cd(C₉H₆N₇)₂(H₂O)₂]_n, (II), the Cd^II dication resides on a centre of inversion in an octahedral {N₄O₂} environment. In the equatorial plane, the Cd^II polyhedron is built up from four N atoms of two kinds, namely of trans‐coordinating tr and tz fragments [Cd—N = 2.2926 (17) and 2.3603 (18) Å], and the coordinating aqua ligands occupy the two apical sites. The metal centres are separated at a distance of 11.1006 (7) Å by means of the double‐bridging tetrazolate anion, L⁻, forming a chain structure. The water ligands and tz fragments interact with one another, like a double hydrogen‐bond donor–acceptor synthon, leading to a hydrogen‐bonded three‐dimensional array.     

Copper‐Catalyzed Enantioselective Markovnikov Protoboration of α‐Olefins Enabled by a Buttressed N‐Heterocyclic Carbene Ligand

Reported is a highly enantioselective copper‐catalyzed Markovnikov protoboration of unactivated terminal alkenes. A variety of simple and abundant feedstock α‐olefins bearing a diverse array of functional groups and heterocyclic substituents can be used as substrates, and the reaction proceeds under mild reaction conditions at ambient temperature to provide expedient access to enantioenriched alkylboronic esters in good regioselectivity and with excellent enantiocontrol. Critical to the success of the protocol was the development and application of a novel, sterically hindered N‐heterocyclic carbene, (R,R,R,R)‐ANIPE, as the ligand for copper.