Iridium(III) carbene complexes as potent girdin inhibitors against metastatic cancers.

Many cancer-driving protein targets remain undruggable due to a lack of binding molecular scaffolds. In this regard, octahedral metal complexes with unique and versatile three-dimensional structures have rarely been explored as inhibitors of undruggable protein targets. Here, we describe antitumor iridium(III) pyridinium-N-heterocyclic carbene complex 1a, which profoundly reduces the viability of lung and breast cancer cells as well as cancer patient-derived organoids at low micromolar concentrations. Compound 1a effectively inhibits the growth of non-small-cell lung cancer and triple-negative breast cancer xenograft tumors, impedes the metastatic spread of breast cancer cells, and can be modified into an antibody-drug conjugate payload to achieve precise tumor delivery in mice. Identified by thermal proteome profiling, an important molecular target of 1a in cellulo is Girdin, a multifunctional adaptor protein that is overexpressed in cancer cells and unequivocally serves as a signaling hub for multiple pivotal oncogenic pathways. However, specific small-molecule inhibitors of Girdin have not yet been developed. Notably, 1a exhibits high binding affinity to Girdin with a Kd of 1.3 µM and targets the Girdin-linked EGFR/AKT/mTOR/STAT3 cancer-driving pathway, inhibiting cancer cell proliferation and metastatic activity. Our study reveals a potent Girdin-targeting anticancer compound and demonstrates that octahedral metal complexes constitute an untapped library of small-molecule inhibitors that can fit into the ligand-binding pockets of key oncoproteins.

Nonalternant Nanographenes Containing N-Centered Cyclopenta[ef]heptalene and Aza[7]Helicene Units.

Introducing helical subunits into negatively curved π-systems has a significant effect on both the molecular geometry and photophysical properties; however, the synthesis of these helical π-systems embedded with nonbenzenoid subunits remains challenging due to the high strain deriving from both the curvature and helix. Here, we report a family of nonalternant nanographenes containing a nitrogen (N)-doped cyclopenta[ef]heptalene unit. Among them, CPH-2 and CPH-3 can be viewed as hybrids of benzoannulated cyclopenta[ef]heptalene and aza[7]helicene. The crystal structures revealed a saddle geometry for CPH-1, a saddle-helix hybrid for CPH-2, and a twist-helix hybrid for CPH-3. Experimental measurements and theoretical calculations indicate that the saddle moieties in CPHs undergo flexible conformational changes at room temperature, while the aza[7]helicene subunit exhibits a dramatically increased racemization energy barrier (78.2 kcal mol-1 for CPH-2, 143.2 kcal mol-1 for CPH-3). The combination of the nitrogen lone electron pairs of the N-doped cyclopenta[ef]heptalene unit with the twisted helix fragments results in rich photophysics with distinctive fluorescence and phosphorescence in CPH-1 and CPH-2 and the similar energy fluorescence and phosphorescence in CPH-3. Both enantiopure CPH-2 and CPH-3 display distinct circular dichroism (CD) signals in the UV-vis range. Notably, compared to the reported fully π-extended helical nanographenes, CPH-3 exhibits excellent chiroptical properties with a |gabs| value of 1.0 × 10-2 and a |glum| value of 7.0 × 10-3; these values are among the highest for helical nanographenes.

Benzo-Extended Heli(aminoborane)s: Inner Rim BN-Doped Helical Molecular Carbons with Remarkable Chiroptical Properties.

Atomically precise synthesis of three-dimensional boron-nitrogen (BN)-based helical structures constitutes an undeveloped field with challenges in synthetic chemistry. Herein, we synthesized and comprehensively characterized a new class of helical molecular carbons, named benzo-extended [n]heli(aminoborane)s ([n]HABs), in which the helical structures consisted of n = 8 and n = 10 ortho-condensed conjugated rings with alternating BN atoms at the inner rims. X-ray crystallographic analysis, photophysical studies, and density functional theory calculations revealed the unique characteristics of this novel [n]HAB system. Owing to the high enantiomerization energy barriers, the optical resolution of [8]HAB and [10]HAB was achieved with chiral high-performance liquid chromatography. The isolated enantiomers of [10]HAB exhibited record absorption and luminescence dissymmetry factors (|gabs|=0.061; |glum|=0.048), and boosted CPL brightness up to 292 M-1 cm-1, surpassing most helicene derivatives, demonstrating that the introduction of BN atoms into the inner positions of helicenes can increase both the |gabs| and |glum| values.

Predictions of photophysical properties of phosphorescent platinum(II) complexes based on ensemble machine learning approach.

Cyclometalated Pt(II) complexes are popular phosphorescent emitters with color-tunable emissions. To render their practical applications as organic light-emitting diodes emitters, it is required to develop Pt(II) complexes with high radiative decay rate constant and photoluminescence (PL) quantum yield. Here, a general protocol is developed for accurate predictions of emission wavelength, radiative decay rate constant, and PL quantum yield based on the combination of first-principles quantum mechanical method, machine learning, and experimental calibration. A new dataset concerning phosphorescent Pt(II) emitters is constructed, with more than 200 samples collected from the literature. Features containing pertinent electronic properties of the complexes are chosen and ensemble learning models combined with stacking-based approaches exhibit the best performance, where the values of squared correlation coefficients are 0.96, 0.81, and 0.67 for the predictions of emission wavelength, PL quantum yield and radiative decay rate constant, respectively. The accuracy of the protocol is further confirmed using 24 recently reported Pt(II) complexes, which demonstrates its reliability for a broad palette of Pt(II) emitters.

Sterically Hindered Tetradentate [Pt(O

Described here are sterically hindered tetradentate [Pt(O^N^C^N)] emitters (Pt-1, Pt-2, and Pt-3) developed for stable and high-performance green phosphorescent organic light-emitting diodes (OLEDs). These Pt(II) emitters exhibit strong saturated green phosphorescence (λmax = 517-531 nm) in toluene and mCP thin films with emission quantum yields as high as 0.97, radiative rate constants (kr) as high as 4.4-5.3 × 105 s-1 and reduced excimer emission, and with a preferential horizontally oriented transition dipole ratio of up to 84%. Theoretical calculations show that p-(hetero)arene substituents at the periphery of the ligand scaffolds in Pt-1, Pt-2, and Pt-3 can i) enhance the spin-orbit coupling (SOC) between the lower singlet excited states and the T1 state, and S0→Sn (n = 1 or 2) transition dipole moment, and ii) introducing additional SOC activity and the bright 1ILCT[π(carbazole)→π*(N^C^N)] excited state (Pt-2 and Pt-3), which are the main contributors to the increased kr values. Utilizing these tetradentate Pt(II) emitters, green phosphorescent OLEDs are fabricated with narrow-band electroluminescence (FWHM down to 36 nm), high external quantum efficiency, current efficiency up to 27.6% and 98.7 cd A-1, and an unprecedented device lifetime (LT95) of up to 9270 h at 1000 cd m-2 under laboratory conditions.

Strong metal-metal Pauli repulsion leads to repulsive metallophilicity in closed-shell d8 and d10 organometallic complexes.

Metallophilicity is defined as the interaction among closed-shell metal centers, the origin of which remains controversial, particularly for the roles of spd orbital hybridization (mixing of the spd atomic orbitals of the metal atom in the molecular orbitals of metal complex) and the relativistic effect. Our studies reveal that at close M-M' distances in the X-ray crystal structures of d8 and d10 organometallic complexes, M-M' closed-shell interactions are repulsive in nature due to strong M-M' Pauli repulsion. The relativistic effect facilitates (n + 1)s-nd and (n + 1)p-nd orbital hybridization of the metal atom, where (n + 1)s-nd hybridization induces strong M-M' Pauli repulsion and repulsive M-M' orbital interaction, and (n + 1)p-nd hybridization suppresses M-M' Pauli repulsion. This model is validated by both DFT (density functional theory) and high-level coupled-cluster singles and doubles with perturbative triples computations and is used to account for the fact that the intermolecular or intramolecular Ag-Ag' distance is shorter than the Au-Au' distance, where a weaker Ag-Ag' Pauli repulsion plays an important role. The experimental studies verify the importance of ligands in intermolecular interactions. Although the M-M' interaction is repulsive in nature, the linear coordination geometry of the d10 metal complex suppresses the L-L' (ligand-ligand) Pauli repulsion while retaining the strength of the attractive L-L' dispersion, leading to a close unsupported M-M' distance that is shorter than the sum of the van der Waals radius (rvdw) of the metal atoms.

Platinum(II) N-heterocyclic carbene complexes arrest metastatic tumor growth.

Vimentin is a cytoskeletal intermediate filament protein that plays pivotal roles in tumor initiation, progression, and metastasis, and its overexpression in aggressive cancers predicted poor prognosis. Herein described is a highly effective antitumor and antimetastatic metal complex [PtII(C^N^N)(NHC2Bu)]PF6 (Pt1a; HC^N^N = 6-phenyl-2,2'-bipyridine; NHC= N-heterocyclic carbene) that engages vimentin via noncovalent binding interactions with a distinct orthogonal structural scaffold. Pt1a displays vimentin-binding affinity with a dissociation constant of 1.06 µM from surface plasmon resonance measurements and fits into a pocket between the coiled coils of the rod domain of vimentin with multiple hydrophobic interactions. It engages vimentin in cellulo, disrupts vimentin cytoskeleton, reduces vimentin expression in tumors, suppresses xenograft growth and metastasis in different mouse models, and is well tolerated, attributable to biotransformation to less toxic and renal-clearable platinum(II) species. Our studies uncovered the practical therapeutic potential of platinum(II)‒NHC complexes as effective targeted chemotherapy for combating metastatic and cisplatin-resistant cancers.

Trapdoor Deformity Correction Post Nasal Bilobed Flaps for Basal Cell Carcinoma Reconstruction With Multiple Laser Modalities.

ABSTRACT: In case of excision of nasal basal cell carcinoma (BCC), bilobed flaps are considered the criterion standard of reconstruction for defect less than 15 mm in size. However, there is still a risk of trapdoor deformity formation, of which its treatment is less discussed. A 44-year-old woman who was diagnosed with nasal BCC and underwent tumor excision with bilobed flap reconstruction presented with trapdoor deformity postoperatively. The computed Vancouver Scar Scale was 7. After early intervention of multiple laser modalities, including 2 sessions of 585-nm pulsed dye laser with a fluence of 9 J/cm2, pulse duration of 6 milliseconds, and spot size of 6 mm, 2940-nm Er-yttrium aluminum garnet (YAG) laser with a pulse energy of 800-900 mJ, repetition rate of 8-9 Hz, and laser spot size of 3-7 mm, and 5 sessions of 1064-nm Nd:YAG fractional picosecond laser with a pulse energy of 2.30-2.70 mJ, repetition rate of 8 Hz, and laser spot size of 6 mm from 5 to 23 weeks postoperatively, the Vancouver Scar Scale score improved to 1, with significant reduction of trapdoor scar erythema and puffiness. Although BCC is often curable, tumor excision causes unsatisfactory appearance satisfaction problem, owing to the apparent location of the lesion. Factors, such as sebaceous tissue thickness, reconstruction over multiple aesthetic subunits of nose, and damage to nasal cartilage framework structure during tumor removal, may increase the risk of trapdoor formation. Early intervention with multiple laser treatment can significantly revise the deformity.

Nonalternant B,N-Embedded Helical Nanographenes Containing Azepines: Programmable Synthesis, Responsive Chiroptical Properties and Spontaneous Resolution into a Single-Handed Helix.

Heteroatom-embedded helical nanographenes (NGs) constitute an important and appealing class of intrinsically chiral materials. In this work, a series of B,N-embedded helical NGs bearing azepines was synthesized via stepwise regioselective cyclodehydrogenation. First, the phenyl- or nitrogen-bridged dimers were efficiently clipped into highly congested model compounds 1 and 2. Later, the controllable Scholl reactions of the tetraphenyl-tethered precursor generated 1, 7 or 8 new C‒C bonds, thereby establishing a robust method for the preparation of nonalternant BN-HNGs with up to 31 fused rings. The helical bilayer nature was unambiguously verified by X-ray diffraction analysis. The helical chirality was transferred to the stereogenic boron centers upon fluoride coordination, with a concave-concave structure to comply with the bilayer skeleton. Notably, the largest nonalternant BN-HNG (6) spontaneously resolved into a homochiral 41 helix structure as a molecular spiral staircase during crystallization via conglomerate formation at the single-crystal scale. The large twisted C2-symmetric pi-surface and the dynamic chiral skeleton induced by curved azepines might have synergistic effects on self-recognition of enantiomers of 6 to achieve the intriguing spontaneous resolution behavior. The chiroptical properties of the enantiomer of 6 were further investigated, revealing that 6 had a strong chiroptical response in the visible range (400-700 nm).

Dinuclear Cyclometalated Pincer Nickel(II) Complexes with Metal-Metal-to-Ligand Charge Transfer Excited States and Near-Infrared Emission.

Facile non-radiative decay of low-lying metal-centered (MC) d-d excited states has been well documented to pose a significant obstacle to the development of phosphorescent NiII complexes due to substantial structural distortions between the d-d excited state and the ground state. Herein, we prepared a series of dinuclear Ni2II,II complexes by using strong σ-donors, carbene-phenyl-carbene (CNHC^Cphenyl^CNHC) pincer ligands, and prepared their dinuclear Pt2II,II and Pd2II,II analogues. Dinuclear Ni2II,II complexes bridged by formamidinate/α-carbolinato ligand exhibit short Ni-Ni distances of 2.947-3.054 Å and singlet metal-metal-to-ligand charge transfer (1MMLCT) transitions at 500-550 nm. Their 1MMLCT absorption energies are red-shifted relative to the Pt2II,II and Pd2II,II analogues at ~450 nm and ≤420 nm respectively. One-electron oxidation of these Ni2II,II complexes produces valence-trapped dinuclear Ni2II,III species, which are characterized by EPR spectroscopy. Upon photoexcitation, these Ni2II,II complexes display phosphorescence (τ=2.6-8.6 µs) in the NIR (800-1400nm) spectral region in 2-MeTHF and in solid state at 77 K, which is insensitive to π-conjugation of the coordinated [CNHC^Cphenyl^CNHC] ligand. Combined with DFT calculations, the NIR emission is assigned to originate from the 3dd excited state. Studies have found that the dinuclear Ni2II,II complex can sensitize the formation of singlet oxygen and catalyze the oxidation of cyclo-dienes under light irradiation.

Red-Shifting B12-Dependent Photoreceptor Protein via Optical Coupling for Inducible Living Materials.

Cobalamin (B12)-dependent photoreceptors are gaining traction in materials synthetic biology, especially for optically controlling cell-to-cell adhesion in living materials. However, these proteins are mostly responsive to green light, limiting their deep-tissue applications. Here, we present a general strategy for shifting photoresponse of B12-dependent photoreceptor CarHC from green to red/far-red light via optical coupling. Using thiol-maleimide click chemistry, we labeled cysteine-containing CarHC mutants with SulfoCyanine5 (Cy5), a red light-capturing fluorophore. The resulting photoreceptors not only retained the ability to tetramerize in the presence of adenosylcobalamin (AdoB12), but also gained sensitivity to red light; labeled tetramers disassembled on red light exposure. Using genetically encoded click chemistry, we assembled the red-shifted proteins into hydrogels that degraded rapidly in response to red light. Furthermore, Saccharomyces cerevisiae cells were genetically engineered to display CarHC variants, which, alongside in situ Cy5 labeling, led to living materials that could assemble and disassemble in response to AdoB12 and red light, respectively. These results illustrate the CarHC spectrally tuned by optical coupling as a versatile motif for dynamically controlling cell-to-cell interactions within engineered living materials. Given their prevalence and ecological diversity in nature, this spectral tuning method will expand the use of B12-dependent photoreceptors in optogenetics and living materials.

Step-by-Step Electrocrystallization Processes to Make Multiblock Magnetic Molecular Heterostructures.

Assembling conductive or magnetic heterostructures by bulk inorganic materials is important for making functional electronic or spintronic devices, such as semiconductive p-doped and n-doped silicon for P-N junction diodes, alternating ferromagnetic and nonmagnetic conductive layers used in giant magnetoresistance (GMR). Nonetheless, there have been few demonstrations of conductive or magnetic heterostructures made by discrete molecules. It is of fundamental interest to prepare and investigate heterostructures based on molecular conductors or molecular magnets, such as single-molecule magnets (SMMs). Herein, we demonstrate the fabrication of a series of molecular heterostructures composed of (TTF)2M(pdms)2 (TTF = tetrathiafulvalene, M = Co(II), Zn(II), Ni(II), H2pdms = 1,2-bis(methanesulfonamido)benzene) multiple building blocks through a well-controlled step-by-step electrocrystallization growth process, where the Co(pdms)2, Ni(pdms)2, and Zn(pdms)2 anionic complex is a SMM, paramagnetic, and diamagnetic molecule, respectively. Magnetic and SMM properties of the heterostructures were characterized and compared to the parentage (TTF)2Co(pdms)2 complex. This study presents the first methodology for creating molecule-based magnetic heterostructural systems by electrocrystallization.

An anticancer gold(III)-activated porphyrin scaffold that covalently modifies protein cysteine thiols.

Cysteine thiols of many cancer-associated proteins are attractive targets of anticancer agents. Herein, we unequivocally demonstrate a distinct thiol-targeting property of gold(III) mesoporphyrin IX dimethyl ester (AuMesoIX) and its anticancer activities. While the binding of cysteine thiols with metal complexes usually occurs via M-S bond formation, AuMesoIX is unique in that the meso-carbon atom of the porphyrin ring is activated by the gold(III) ion to undergo nucleophilic aromatic substitution with thiols. AuMesoIX was shown to modify reactive cysteine residues and inhibit the activities of anticancer protein targets including thioredoxin, peroxiredoxin, and deubiquitinases. Treatment of cancer cells with AuMesoIX resulted in the formation of gold-bound sulfur-rich protein aggregates, oxidative stress-mediated cytotoxicity, and accumulation of ubiquitinated proteins. Importantly, AuMesoIX exhibited effective antitumor activity in mice. Our study has uncovered a gold(III)-induced ligand scaffold reactivity for thiol targeting that can be exploited for anticancer applications.

[Effect of Zhenwu Decoction on electrical remodeling of cardiomyocytes in heart failure via I_(to)/Kv channels].

This study aimed to investigate the underlying mechanism of Zhenwu Decoction in the treatment of heart failure by regulating electrical remodeling through the transient outward potassium current(I_(to))/voltage-gated potassium(Kv) channels. Five normal SD rats were intragastrically administered with Zhenwu Decoction granules to prepare drug-containing serum, and another seven normal SD rats received an equal amount of distilled water to prepare blank serum. H9c2 cardiomyocytes underwent conventional passage and were treated with angiotensin Ⅱ(AngⅡ) for 24 h. Subsequently, 2%, 4%, and 8% drug-containing serum, simvastatin(SIM), and BaCl_2 were used to interfere in H9c2 cardiomyocytes for 24 h. The cells were divided into a control group [N, 10% blank serum + 90% high-glucose DMEM(DMEM-H)], a model group(M, AngⅡ + 10% blank serum + 90% DMEM-H), a low-dose Zhenwu Decoction-containing serum group(Z1, AngⅡ + 2% drug-containing serum of Zhenwu Decoction + 8% blank serum + 90% DMEM-H), a medium-dose Zhenwu Decoction-containing serum group(Z2, AngⅡ + 4% drug-containing serum of Zhenwu Decoc-tion + 6% blank serum + 90% DMEM-H), a high-dose Zhenwu Decoction-containing serum group(Z3, AngⅡ + 8% drug-containing serum of Zhenwu Decoction + 2% blank serum + 90% DMEM-H), an inducer group(YD, AngⅡ + SIM + 10% blank serum + 90% DMEM-H), and an inhibitor group(YZ, AngⅡ + BaCl_2 + 10% blank serum + 90% DMEM-H). The content of ANP in cell extracts of each group was detected by ELISA. The relative mRNA expression levels of ANP, Kv1.4, Kv4.2, Kv4.3, DPP6, and KChIP2 were detected by real-time quantitative PCR. The protein expression of Kv1.4, Kv4.2, Kv4.3, DPP6, and KChIP2 was detected by Western blot. I_(to) was detected by the whole cell patch-clamp technique. The results showed that Zhenwu Decoction at low, medium, and high doses could effectively reduce the surface area of cardiomyocytes. Compared with the M group, the Z1, Z2, Z3, and YD groups showed decreased ANP content and mRNA level, increased protein and mRNA expression of Kv4.2, Kv4.3, DPP6, and KChIP2, and decreased protein and mRNA expression of Kv1.4, and the aforementioned changes were the most notable in the Z3 group. Compared with the N group, the Z1, Z2, and Z3 groups showed significantly increased peak current and current density of I_(to). The results indicate that Zhenwu Decoction can regulate myocardial remodeling and electrical remodeling by improving the expression trend of Kv1.4, Kv4.2, Kv4.3, KChIP2, and DPP6 proteins and inducing I_(to) to regulate Kv channels, which may be one of the mechanisms of Zhenwu Decoction in treating heart failure and related arrhythmias.

Three-Component Multiblock 1D Supramolecular Copolymers of Ir(III) Complexes with Controllable Sequences.

Multicomponent supramolecular block copolymers (BCPs) have attracted much attention due to their potential functionalities, but examples of three-component supramolecular BCPs are rare. Herein, we report the synthesis of three-component multiblock 1D supramolecular copolymers of Ir(III) complexes 1-3 by a sequential seeded supramolecular polymerization approach. Precise control over the kinetically trapped species via the pathway complexity of the monomers is the key to the successful synthesis of BCPs with up to 9 blocks. Furthermore, 5-block BCPs with different sequences could be synthesized by changing the addition order of the kinetic species during a sequentially seeded process. The corresponding heterogeneous nucleation-elongation process has been confirmed by the UV/Vis absorption spectra, and each segment of the multiblock copolymers could be characterized by both TEM and SEM. Interestingly, the energy transfer leads to weakened emission of 1-terminated and enhanced emission of 3-terminated BCPs. This study will be an important step in advancing the synthesis and properties of three-component BCPs.

A Convergent, Modular Approach to Trifluoromethyl-Bearing 5-Membered Rings via Catalytic C(sp3 )-H Activation.

Trifluoromethyl-bearing 5-membered rings are prevalent in bioactive molecules, but modular approaches to these compounds by functionalization of robust C(sp3 )-H bonds in a direct and selective manner are extremely challenging. Herein we report the rhodium-catalyzed α-CF3 -α-alkyl carbene insertion into C(sp3 )-H bonds of a broad range of substrates to access 7 types of CF3 -bearing saturated 5-membered carbo- and heterocycles. The reaction is particularly effective for benzylic C-H insertion exerting good site-, diastereo- and enantiocontrol, and applicable to the synthesis of chiral CF3 analogues of bioactive molecules. Ruthenium α-CF3 -α-alkyl carbene complexes underwent stoichiometric reactions to give C-H insertion products, lending evidence for the involvement of metal α-CF3 -α-alkyl carbene species in the catalytic cycle. DFT calculations revealed that the π⋅⋅⋅π attraction and intra-carbene C-H⋅⋅⋅F hydrogen bond elucidate the origin of selectivity of the benzylic C-H insertion reactions.

Controlled Self-assembly of Gold(I) Complexes by Multiple Kinetic Aggregation States with Nonlinear Optical and Waveguide Properties.

Introduction of multiple kinetic aggregation states (Aggs) into the self-assembly pathway could bring complexity and flexibility to the self-assemblies, which is difficult to realize due to the delicate equilibria established among different Aggs bonded by weak noncovalent interactions. Here, we describe a series of chiral and achiral d10 AuI bis(N-heterocyclic carbene, NHC) complexes, and the achiral complex could undergo self-assembly with multiple kinetic Aggs. Generation of multiple kinetic Aggs was realized by applying chiral or achiral seeds exhibiting large differences in elongation temperatures for their respective cooperative self-assembly processes. We further showed that the chiral AuI self-assemblies having non-centrosymmetric packing forms exhibit nonlinear optical response of second harmonic generation (SHG), while the SHG signal is absent in the achiral analogue. The crystalline achiral AuI self-assemblies could function as optical waveguides with strong emission polarization.

Chiral Iron Porphyrins Catalyze Enantioselective Intramolecular C(sp3 )-H Bond Amination Upon Visible-Light Irradiation.

Iron-catalyzed asymmetric amination of C(sp3 )-H bonds is appealing for synthetic applications due to the biocompatibility and high earth abundance of iron, but examples of such reactions are sparse. Herein we describe chiral iron complexes of meso- and ß-substituted-porphyrins that can catalyze asymmetric intramolecular C(sp3 )-H amination of aryl and arylsulfonyl azides to afford chiral indolines (29 examples) and benzofused cyclic sulfonamides (17 examples), respectively, with up to 93 % ee (yield: up to 99 %) using 410 nm light under mild conditions. Mechanistic studies, including DFT calculations, for the reactions of arylsulfonyl azides reveal that the Fe(NSO2 Ar) intermediate generated in situ under photochemical conditions reacts with the C(sp3 )-H bond through a stepwise hydrogen atom transfer/radical rebound mechanism, with enantioselectivity arising from cooperative noncovalent interactions between the Fe(NSO2 Ar) unit and the peripheral substituents of the chiral porphyrin scaffold.

Fe-BPsalan Complex-Catalyzed Asymmetric [4 + 2] Cycloaddition of Cyclopentadiene with α,ß-Unsaturated Heterocycles.

An efficient iron-catalyzed asymmetric [4 + 2] cycloaddition of cyclopentadiene with α,ß-unsaturated acyl imidazoles or 2-cinnamoylisoindoline-1,3-dione derivatives was developed to afford the addition products in high yield and selectivity. Interestingly, the absolute structures of the addition products were controlled by the auxiliaries via different coordination modes with the same type of catalyst.

Transition metal complexes with functionalized indenyl phosphine ligands: structures and catalytic properties.

Transition-metal indenyl complexes usually exhibit different reactivities compared with their cyclopentadienyl analogues. Up to now, at least 10 metal-indenyl bonding modes have been reported. Because of the "indenyl effect", transition-metal indenyl complexes usually show enhanced reactivity in substitution and related reactions. This review provides an overview on the use and impact of indenyl phosphines in organometallic chemistry and transition-metal-catalysed reactions in the recent two decades. Some cationic and zwitterionic metal complexes supported by P,N-substituted indene or indenide ligands are described. They have been reported to induce the cleavage of E-H (E = H, Si and B) bonds and can be used as catalysts for addition of E-H bonds to unsaturated substrates. 2-Aryl indenyl phosphine ligands L3-L11 have been proven to be a class of versatile ligands for palladium-catalysed C-C and C-N cross-coupling reactions. Moreover, optically active tethered indenyl phosphine ligands can have better stereoselective control over the chirality arising at the metal center in the oxidative addition of their rhodium complexes with alkyl halides.