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New dinuclear Au(I), Au(II) and Au(III) complexes containing (CF2 )n bridging chains were obtained. Metallomacrocycles [Au2 {μ-(CF2 )4 }{μ-diphosphine}] show an uncommon figure-eight structure, the helicity inversion barrier of which is influenced by aurophilic interactions and steric constraints imposed by the diphosphine. Halogenation of LAu(CF2 )4 AuL (L=PPh3 , PMe3 , (dppf)1/2 , (binap)1/2 ) gave [Au(II)]2 species, some of which display unprecedented folded structures with Au-Au bonds. Aurophilic interactions facilitate this oxidation process by preorganizing the starting [Au(I)]2 complexes and lowering its redox potential. The obtained [Au(II)]2 complexes undergo thermal or photochemical elimination of R3 PAuX to give Au(III) perfluorinated auracycles. Evidence of a radical mechanism for these decomposition reactions was obtained.

The catalytic ortho to para transposition of a silyl group in aniline derivatives is described. [RuCl2(p-cymene)]2/BINAP in conjunction with a Cu(OAc)2 additive serves as a potent catalytic system. This method is also applicable to the isomerization of 2-silylpyrrole derivatives to the corresponding 3-silyl isomers.

A C1-symmetric chiral bisphosphine, FcPh-Binap (1), which possesses a single diferrocenylphosphino moiety together with a conventional Ph2P-substituent, was prepared in enantiomerically pure forms....

We successfully fabricated a novel sensing platform, a Membrane-type Surface stress Sensor (MSS) coated with copper(I) complex bearing phen and BINAP ligands, [Cu(phen)((±)-BINAP)]PF6 (1, phen = 1,...

In this article, we report a preference of homochiral-type ligation of BINAP that produces SS-type ligand assembly onto the Au11 clusters protected by diphosphine S,S-DIOP. The Au11 clusters synthesized and isolated are Au11(S,S-DIOP)4(rac-/R-/S-BINAP), and their optical/chiroptical responses are characterized. Absorption spectra of these Au11 clusters are almost identical to each other, but their CD profiles are dependent on the handedness of BINAP. In Au11(S,S-DIOP)4(rac-BINAP), the yield of S-BINAP or R-BINAP coordination is roughly comparable, but we found a small but distinctive preference in the S-BINAP ligation; that is, homochiral-type (SS-type) ligand assembly formation. Quantum chemical calculations for simplified model clusters suggest equal contributions of S- and R-form BINAP coordination. The experimentally-observed preference of homochiral-type ligation can then be due to that of the whole ligand structures and assemblies involving interligand interactions. Chiral sorting and amplification processes through the assembly control of homochirality or heterochirality are of primary importance for the development of enantioselective reactions, so we anticipate this finding will contribute to further understanding of such processes based on various metal clusters with chiral ligands.

Ligand-controlled palladium-catalyzed divergent synthesis of isonitriles and nitriles from benzylic carbonates and TMSCN has been developed. The BINAP- or DPEphos-ligated palladium catalyst selectively provides the corresponding benzylic isonitriles, whereas their regioisomers, benzylic nitriles, are formed exclusively under phosphine ligand-free conditions. Mechanistic studies reveal that isonitrile is the primary product under both conditions, but it is isomerized into nitrile in the absence of ancillary phosphine ligands.

We report full details of the synthesis and characterization of monohydride-dichloro rhodium(III) complexes bearing chiral diphosphine ligands, such as (S)-BINAP, (S)-DM-SEGPHOS, and (S)-DTBM-SEGPHOS, producing cationic triply chloride bridged dinuclear rhodium(III) complexes (1 a: (S)-BINAP; 1 b: (S)-DM-SEGPHOS) and a neutral mononuclear monohydride-dichloro rhodium(III) complex (1 c: (S)-DTBM-SEGPHOS) in high yield and high purity. Their solid state structure and solution behavior were determined by crystallographic studies as well as full spectral data, including DOSY NMR spectroscopy. Among these three complexes, 1 c has a rigid pocket surrounded by two chloride atoms bound to the rhodium atom together with one tBu group of (S)-DTBM-SEGPHOS for fitting to simple olefins without any coordinating functional groups. Complex 1 c exhibited superior catalytic activity and enantioselectivity for asymmetric hydrogenation of exo-olefins and olefinic substrates. The catalytic activity of 1 c was compared with that of well-demonstrated dihydride species derived in situ from rhodium(I) precursors such as [Rh(cod)Cl]2 and [Rh(cod)2 ]+ [BF4 ]- upon mixing with (S)-DTBM-SEGPHOS under dihydrogen.

A photoredox protocol that uses a heteroleptic Cu (I) complex, [Cu­(dq)­(BINAP)]­BF4, has been developed for the photodeprotection of benzenesulfonyl-protected N-heterocycles. A range of substrates was examined, including indazoles, indoles, pyrazoles, and benzimidazole, featuring both electron-rich and electron-deficient substituents, giving good yields of the N-heterocycle products with broad functional group tolerance. This transformation was also found to be amenable to flow reaction conditions.

BACKGROUND: Aromatic thioether derivatives exist widely in natural products and have significant applications in modern synthesis and the pharmaceutical industry; for example, 2‐sulfanylphenols and arylthioquinones are important intermediates in the processing of anticancer, antibiotic, antivirus and antimalarial drugs. Direct C─H hydroxylation was considered as one of the efficient methods for the synthesis of these compounds. Homogeneous transition metal catalysts usually were used through a cross‐coupling of halogen‐substituted phenols with thiophenols. However, from the perspectives of sustainable development and easy recovery, it is necessary to develop an efficient and recoverable catalytic system to realize the synthesis of aromatic thioether derivatives with good efficiency and recyclability. RESULTS: The heterogeneous catalyst [Cu(binap)I]₂@HT in the present work showed good catalytic activity for the C─H hydroxylation of benzenethiol and phenylboronic acid. The catalytic system was tolerant to various substituents including alkyl, alkoxy, ester, halogen or trifluoromethyl on the phenyl ring of the thiophenols or arylboric acids. In addition to electron‐donating groups, the products with strong electron‐withdrawing groups, such as methyl formylate and trifluoromethyl also were achieved with good yields at 90 °C for 12 h (68% and 66%, respectively). Repeated experiment results showed that the catalyst could be reused at least five times without obvious decrease in catalytic activity. CONCLUSION: A BINAP‐Cu complex supported on hydrotalcite was prepared and used as a heterogeneous catalyst for the C─H activation of thiophenol under mild reaction conditions. Through a cascade C─H hydroxylation and further oxidation process, 2‐Sulfanylphenols and arylthioquinones could be obtained with moderate‐to‐good yields for a series of 2‐(phenylthio)phenol derivatives using the heterogeneous catalyst [Cu(binap)I]₂@HT. In addition, this heterogeneous catalyst showed good recylbility. © 2020 Society of Chemical Industry

N-(4-(3-(6-(Difluoromethyl)pyridin-2-yl)-1H-pyrrolo[3,2-b]pyridin-2-yl)pyridin-2-yl)acetamide (5) is a potent inhibitor of TGFβRI kinase that provides durable antitumor activity when combined with ...

Luminescent cuprous complexes are an important class of coordination compounds due to their relative abundance, low cost and ability to display excellent luminescence. The heteroleptic cuprous complex solvate rac-(acetonitrile-κN)(3-aminopyridine-κN)[2,2′-bis(diphenylphosphanyl)-1,1′-binaphthyl-κ2 P,P′]copper(I) hexafluoridophosphate dichloromethane monosolvate, [Cu(C5H6N2)(C2H3N)(C44H32P2)]PF6·CH2Cl2, conventionally abbreviated as [Cu(3-PyNH2)(CH3CN)(BINAP)]PF6·CH2Cl2, (I), where BINAP and 3-PyNH2 represent 2,2′-bis(diphenylphosphanyl)-1,1′-binaphthyl and 3-aminopyridine, respectively, is described. In this complex solvate, the asymmetric unit consists of a cocrystallized dichloromethane molecule, a hexafluoridophosphate anion and a complete racemic heteroleptic cuprous complex cation in which the cuprous centre, in a tetrahedral CuP2N2 coordination, is coordinated by two P atoms from the BINAP ligand, one N atom from the 3-PyNH2 ligand and another N atom from a coordinated acetonitrile molecule. The UV–Vis absorption and photoluminescence properties of this heteroleptic cuprous complex have been studied on polycrystalline powder samples, which had been verified by powder X-ray diffraction before recording the spectra. Time-dependent density functional theory (TD-DFT) calculations and a wavefunction analysis reveal that the orange–yellow phosphorescence emission should originate from intra-ligand (BINAP) charge transfer mixed with a little of the metal-to-ligand charge transfer 3(IL+ML)CT excited state.

Planar-chiral Phanephos, containing the coordinatable P(III), formed P(III)/Tb(III)(hfa)3 hybrid luminophores that successfully emitted characteristic circularly polarised luminescence (CPL) due to 5D4 → 7F5 transitions in solution. On the other hand, BINAP, containing P(III)O as axially chiral ligand, exhibited no detectable CPL with Tb(III)(hfa)3.

Heterocycles represent one of the largest groups of organic moieties with significant medicinal, chemical, and industrial applications. Herein, we report the discovery and development of visible-light-induced, synergistic excited-state copper catalysis using a combination of Cu(IPr)I as a catalyst and rac-BINAP as a ligand, which produces more than 10 distinct classes of heterocycles. The reaction tolerates a broad array of functional groups and complex molecular scaffolds, including derivatives of peptides, natural products, and marketed drugs. Preliminary mechanistic investigation suggests in situ generations of [Cu(BINAP)(2)](+) and [Cu(IPr)(2)](+) catalysts that work cooperatively under visible-light irradiation to facilitate catalytic carbo-aroylation of unactivated alkenes, affording a wide range of useful heterocycles.

Ligand-controlled regiodivergence has been developed for catalytic semireduction of allenamides with excellent chemo- and stereocontrol. This system also provides an example of catalytic regiodivergent semireduction of allenes for the first time. The divergence of the semireduction is enabled by ligand switch with the same palladium pre-catalyst under operationally simple and mild conditions. Monodentate ligand XPhos exclusively promotes selective 1,2-semireduction to afford allylic amides, while bidentate ligand BINAP completely switched the regioselectivity to 2,3-semireduction, producing (E)-enamide derivatives.

The first catalytic enantioselective ruthenium-catalyzed carbonyl reductive couplings of allene pronucleophiles is described. Using an iodide-modified ruthenium-BINAP-catalyst and O-benzhydryl alkoxyallene 1a, carbonyl (α-alkoxy)allylation occurs from the alcohol or aldehyde oxidation level to form enantiomerically enriched syn-sec,tert-diols. Internal chelation directs intervention of (Z)-σ-alkoxyallylruthenium isomers, which engage in stereospecific carbonyl addition.

A series of dinuclear iridium polyhydride complexes bearing BINAP ligands were synthesized and characterized for use as photocatalysts. The UV–vis absorption spectra of theses complexes exhibit abs...

The smallest spherical carbon nanocage so far, [2.2.2]carbon nanocage, has been synthesized by the cationic rhodium(I)/H8 -binap complex-catalyzed regioselective intermolecular cyclotrimerization of a cis-1-ethynyl-4-arylcyclohexadiene derivative followed by the triple Suzuki-Miyaura cross-couplings with 1,3,5-triborylbenzene and reductive aromatization. This cage molecule is highly strained, and its ring strain is between those of [6] and [5]cycloparaphenylenes. A significant red-shift of an emission maximum was observed, compared with that of known [4.4.4]carbon nanocage. The sequential cyclotrimerizations of a cis-1,4-diethynylcyclohexadiene derivative with the same rhodium(I) catalyst followed by reductive aromatization failed to afford [1.1.1]carbon nanocage; instead, a β-graph-shaped cage molecule was generated.

A series of ionic and neutral alcohol soluble Cu(I) complexes were obtained by reaction of 2-(pentafluorophenyl)-1H-imidazo[4,5-f][1,10]-phenanthroline (ppipH), [Cu(MeCN)4]ClO4 and the chelating diphosphine ligands bis[(2-diphenylphosphino)phenyl]ether (POP), 4,6-bis(diphenylphosphino)phenoxazine (nixantphos), 9,9-dimethyl-4,5-bis(diphenylphosphino)-9H-xanthene (xantphos) and (±)-2,2′-bis(diphenylphosphino)-1,1′-binaphthalene (BINAP) in neutral and strong alkaline media, respectively. Most complexes display moderate to intense luminescence in the solid state and weak, negligible luminescence in EtOH solutions. The aggregation-induced emission for the Cu(I) complexes of flexible POP ligands in ethanol/water system was studied.

Phenyl groups were introduced at the β-positions proximal to the meso-hydroxy moiety in hydroxyporphyrin NiII complexes by oxidized BINAP PdII complexes. Ion-pairing assemblies of deprotonated π-electronic anions, anionic site of which was stabilized by the introduced phenyl moieties with a bulky cation, were formed. They showed charge-by-charge assemblies, assembly modes of which were modulated by the anionic building units.

We report the synthesis and crystal structure determination of two novel chiral gold nanoclusters. By utilizing BINAP, we isolate atomically precise intrinsically chiral Au nanoclusters [Au9(R-/S-BINAP)4](CF3COO)3 and [Au10(R-/S-BINAP)4(p-CF3C6H4C≡C)](CF3COO)3 in high yield with one-pot synthesis. Au9 has C2 geometry, while Au10 is C1 symmetric. Interestingly, reversible interconversion between Au9 and Au10 can be realized by the addition or removal of a RC≡CAu component. The transformation from Au9 to Au10 leads to significant enhancement of CD signals. The maximum anisotropy factor in the visible region of [Au10(BINAP)4(p-CF3C6H4C≡C)]3+ is the hitherto largest (up to 6.6 × 10–3) among gold nanoclusters, which is approximately twice of that of [Au9(BINAP)4]3+. This work demonstrates that the chiroptical activity of gold nanoclusters can be modulated by structural control through the introduction of second ligands.

Diastereoselective direct hydroarylation of glycals with aromatic compounds was realized by use of an iridium/binap catalyst, giving the corresponding C-glycosyl compounds in high yields. The use of binap with the different absolute configuration enabled the stereoselective synthesis of α- or β-C-glycosyl arenes irrespective of the chirality of the glycals....

In this article, the chiroptical responses of Au9 clusters protected by chiral/achiral mixed bidentate phosphine ligands are reported. The mixed phosphine we use is (S)-BINAP/Xantphos in the molar ratio of 1/0 (= pure (S)-BINAP), 3/1, 1/1, or 0/1 (= pure Xantphos), where BINAP and Xantphos represent 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, respectively. Electronic absorption spectra of the clusters are similar between the samples with different molar diphosphine ratios, but the chiroptical activity or g-factor decreases nonlinearly with an increase in the fraction of Xantphos. Quantum chemical calculations and geometrical quantifications based on the Hausdorff chirality measure (HCM) for model Au9 cluster species suggest that (i) two types of metal core structures with pseudo-P- and M-chirality are found, and their appropriate contributions would cancel out the chiroptical response in the low-energy region; (ii) the origin of optical activity in pure (S)-BINAP-protected Au9 clusters can mainly be attributed to the metal core chirality, whereas that of other mixed-ligand protected clusters would be due to the chiral ligand arrangement. This work demonstrates that the modulation of chiroptical activity in Au9 clusters by chiral/achiral mixed-diphosphine ligation is controlled by the difference in the degree of chirality existing in the cluster core and/or the ligand array.

Rhodium complexes of the type HRh(CO)L3 (where L is an N-pyrrolyl phosphine, such as P(NC4H4)3, PPh(NC4H4)2, or PPh2(NC4H4)) were applied in the hydroformylation of less reactive unsaturated substrates, namely allyl acetate, butyl acrylate, methyl acrylate, 2,3-dihydrofuran and vinyl acetate. Even at room temperature, these catalysts enabled complete substrate conversion and high chemoselectivity towards the corresponding aldehydes. High conversion of vinyl acetate (88% in 6 h) to the branched aldehyde was obtained with HRh(CO)[P(NC4H4)3]3 at 25 °C. An increase of the turnover frequency, TOF, up to 2000 mol mol−1 h−1 was achieved in this reaction under 20 bar of syngas (H2/CO = 1) at 80 °C. The introduction of chiral phosphines, BINAP or Ph-BPE, to this system resulted in the production of a branched aldehyde with enantioselectivity, ee, up to 44 and 81%, respectively. High activity combined with high enantioselectivity was achieved due to the formation of the mixed rhodium hydrides HRh(CO)[P(NC4H4)3](BINAP) and HRh(CO)[P(NC4H4)3](Ph-BPE), identified by the NMR method.

Considerable attention has been focused on Cu(i)-diimine-phosphine complexes because of their good room-temperature phosphorescence since 1979, but no attention has been focused on the exploration and exploitation by using them as smart acid-base responsive switching luminescent materials. Herein, the reaction of [Cu(MeCN)4]PF6, 2-(2-naphthyl)-1H-imidazo[4,5-f][1,10]phenanthroline (nimpH) and chelating diphosphine ligands bis[(2-diphenylphosphino)phenyl] ether (POP) and 9,9-dimethyl-4,5-bis(diphenylphosphino)-9H-xanthene (xantphos) or (±)-2,2'-bis(diphenylphosphino)-1,1'-binaphthalene (BINAP) in a 1 : 1 : 1 ratio afforded three ionic [Cu(nimpH)(PP)]PF6 complexes (PP = POP, 1a; xantphos, 2a; BINAP, 3a) and three neutral [Cu(nimp)(PP)] complexes (PP = POP, 1b; xantphos, 2b; BINAP, 3b) in neutral and strong alkaline media, respectively. The non-emissive complexes 1a, 2a and 3a exhibit turn-on luminescence upon exposure to the strong base NaOH and tetrabutylammonium fluoride (TBAF), and the intensely emissive complexes 1b, 2b and 3b display turn-off luminescence upon exposure to trifluoroacetic acid (TFA) in CH2Cl2 solutions. Naked-eye repeatable off-on-off or on-off-on luminescence behaviors of these complexes are observed in CH2Cl2 with reversible base-acid or acid-base responses. On the other hand, the addition of TBAF to neutral complexes 1b, 2b and 3b results in obvious luminescence enhancement, especially for the diluted solutions and complexes with the flexible diphosphine ligand POP. The plausible mechanisms of the above results are discussed.

The first Lewis acid catalyzed stereoconvergent transformation of racemic 2-(hetero)aryl- N-sulfonylaziridines via C-N bond cleavage with nucleophiles is presented. This includes the [3 + 2] annulations with (hetero)aromatic aldehydes and 1,3-disubstituted indoles, asymmetric Friedel-Crafts type reaction with electron-rich (hetero)arenes, and asymmetric aminolysis with amines, providing facile access to chiral 1,3-isoxazolidines, pyrroloindolines, 2-(hetero)arylphenethylamines, and vicinal diamines. This method features a simple and cheaply available complex of Cu(I)-chiral BINAP catalyst, excellent yield and high diastereo- and enantioselectivities, and mild reaction conditions. A mechanism involving type I dynamic kinetic asymmetric transformations (DyKATs) of the racemic aziridines is proposed based on the results of control experiments.

Photoinduced, copper-catalyzed coupling reactions are emerging as a powerful method for generating Csp(3)–Y (Y = C or heteroatom) bonds from alkyl electrophiles and nucleophiles. Corresponding three-component couplings of alkyl electrophiles, olefins, and nucleophiles have the potential to generate an additional Csp(3)–Y bond and to efficiently add functional groups to both carbons of an olefin, which serves as a readily available linchpin. In this report, we establish that a variety of electrophiles and a trifluoromethylthiolate nucleophile can add across an array of olefins (including styrenes and electron-poor olefins) in the presence of CuI/binap and blue-LED irradiation, thereby generating trifluoromethyl thioethers in good yield. The process tolerates a wide range of functional groups, and an initial survey of other nucleophiles (i.e., bromide, cyanide, and azide) suggests that this three-component coupling strategy is versatile. Mechanistic studies are consistent with a photoexcited Cu(I)/binap/SCF(3) complex serving as a reductant to generate an alkyl radical from the electrophile, which likely reacts in turn with the olefin and a Cu(II)/SCF(3) complex to afford the coupling product.

A copper-based photocatalyst, Cu(tmp)(BINAP)BF4, was found to be active in a photoredox Appel-type conversion of alcohols to bromides. The catalyst was identified from a screening of 50 complexes and promoted the transformation of primary and secondary alcohols to their corresponding bromides and carboxylic acids to their anhydrides. The protocol was also amendable and optimized under continuous flow conditions.