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Ring expansion of strained small rings provides an efficient method for the synthesis of various high-value carbocycles and heterocycles. Here we report BF 3 ·Et 2 O as both an activating reagent and fluorine source, enabling ring expansion of phosphirane and P-F bond formation. Treatment of 1-iminylphosphirane complexes with BF 3 ·Et 2 O resulted in 1,2-azaphospholidines, while the reaction of 1-acylphosphirane complexes with BF 3 ·Et 2 O afforded 1,2-dihydrophosphetes. The reaction path was tuned by the nucleophilicity of the N and O atoms toward the intermediate phosphenium cation.

The activation of CS 2 by the 2 H -phosphindole complex with a low-coordinate phosphadiene moiety is reported. The successive hetero-Diels-Alder reaction between 2 H -phosphindoles and CS 2 constructs two bridged rings and one spirocycle simultaneously, affording structurally complex P,S-polycyclic products. The two 2 H -phosphindoles approach the C═S bond in a head-to-head disposition to minimize steric hindrance. This work reveals the unique reactivity of low-coordinate organophosphorus species and their potential applications in small molecule activation.

Herein, we report a facile and highly atom-economic approach to 2-phosphafurans by using simple 2-chloroethylphosphine and acetylenic ketones. The key step of this protocol utilizes the Lewis acidity of electrophilic phosphinidenes to induce an intramolecular cyclization with enones. Dearomative hetero-Diels-Alder reactions of 2-phosphafurans provide two series of bicyclic phosphacycles. This rare synthetic application of Lewis acidity of electrophilic phosphinidene complexes represents a new frontier of phosphinidene chemistry.

Two novel diastereoisomeric P-chirogenic phosphine catalysts, i.e., JiaPhos, which can be easily derived from inexpensive and commercially available starting materials in five chemical operations (totally 4.16g scale), are introduced. To our delight, the JiaPhos catalysts display good performance in enantioselective (4 + 2) annulations involving 3-methylene-2-oxindoles and γ-benzyl allenoates, providing a wide range of 3,3'-spirocyclic oxindoles with good efficiency and enantioselectivity.

We have developed an unprecedented approach for the synthesis of transient 1-phosphafulvenes through three component reactions of phospholes. The generation of 1-phosphafulvenes was demonstrated by in situ [6 + 4] cycloaddition with 2 H -phospholes and [6 + 6] self-dimerization. The [6 + 4] and [6 + 6] reaction pathway could be modulated by the starting ketones and aldehydes. The construction of 1-phosphafulvenes is illustrated by a proposed mechanism combining nucleophilic addition of phospholide to the iminium or isomerized azomethine ylide and a [1,5]-shift of phosphole.

[1 + 2] cycloaddition is a classical reaction between the electrophilic phosphinidene and an alkene. However, a spatial constraint blocks this well-known reaction and enables an unprecedented chemoselective C(sp 2 )-Ar σ-bond insertion of the alkene. The theoretical calculations demonstrate that this C-C bond cleavage is energetically feasible and thermodynamically favored through an electrophilic rearrangement and concomitant 1,9-aryl migration without involving any strained intermediate.

An unusual chemoselective 1,1-addition of α-C 2 -bridged biphospholes to terminal alkynes is reported. The developed protocol provides simple access to the unknown 1,3-diphosphepines, which has potential applications in the coordination and catalyst chemistry. Their Pd and Mo complexes were studied by single-crystal X-ray diffraction analysis. This method features excellent chemoselectivity, high step and atom economy, mild reaction conditions, and wide substrate scope.

A short and efficient route to peri-fused heterocycles has been developed. The transition metal in cooperation with the imino directing group cleaves the C-P bond of the phosphirane, followed by 1,1-insertion of CO and reductive elimination to give a reactive azaphosphacyclohexone derivative. The further dearomatic Diels-Alder reaction of the in situ-generated azaphosphacyclohexone with alkenes provides an array of annulated heterodecalins with high molecular complexity and atomic utilization.

A Ag/P-stereogenic phosphine-complex-catalyzed 1,3-dipolar cycloaddition of azomethine ylides with electron-deficient olefins is reported. In this reaction, highly functionalized pyrrolines with a spiro-quaternary stereogenic center were obtained in good yields (up to 99%) with excellent levels of diastereo- (up to >20:1 dr) and enantioselectivities (up to >99% ee). The chirality of adducts was controlled predominantly by the P-stereogenic phosphines.

A new pair of P-stereogenic ligands with multiple chiral centers were synthesized and used in the copper(I)-catalyzed enatioselective [3 + 2] cycloaddition of iminoesters with alkenes. A variety of highly functionalized pyrrolidines were obtained in excellent yield and enatioselectivity. This is the first example of a pair of P-stereogenic ligands working as pseudoenantiomers to tune the enantio- and diastereoselective 1,3-dipolar cycloaddition, and providing a pair of enantiomerically pure pyrrolidines, respectively.

Using readily available and easy-to-handle reagents, a novel type of nido-carborane-fused phosphole was obtained from a simple procedure. Its crystallographic structure was determined, and DFT calculations have been performed, unraveling the key influence of the zwitterionic structure on the photophysical properties.

Carbon nanotubes (CNTs) and other related CNT-based materials with a high thermal conductivity can be used as promising heat dissipation materials. Meanwhile, the miniaturization and high functionality of portable electronics, such as laptops and mobile phones, are achieved at the cost of overheating the high power-density components. The heat removal for hot spots occurring in a relatively narrow space requires simple and effective cooling methods. Here, an auxiliary passive cooling approach by the aid of a flat plate (aluminum-magnesium alloy) is investigated to accommodate heat dissipation in a narrow space. The cooling efficiency can be raised to 43.5%. The cooling performance of several CNT-based samples is compared under such circumstances. Heat dissipation analyses show that, when there is a nearby plate for cooling assistance, the heat radiation is weakened and natural convection is largely improved. Thus, improving heat radiation by increasing emissivity without reducing natural convection can effectively enhance the cooling performance. Moreover, the decoration of an auxiliary cooling plate with sprayed CNTs can further improve the cooling performance of the entire setup.

The unprecedented 2,2'-bis(azaphosphindole) has been synthesized via a new route. Reaction with NaH afforded a dianion derivative 5, which is easily transformed to alkylated bis(azaphosphindole) or (Z)-P,P,N,N-cisoid diazadiphosphafulvalene. The reaction features good regioselectivity and high steroselectivity. Relatively strong fluorescence is observed with diazadiphosphafulvalenes. The X-ray crystal structure analysis showed that dianion ligand 5 is bonded to two Na atoms in a bridging cis-fashion, which allows the synthesis of diazadiphosphafulvalene in a highly stereoselective approach.

A facile method to synthesize quaternized benzophospholes on gram scale was reported, and the products were isolated by simple filtration. During this research, a series of σ 5 -oxaphosphoranes incorporating polycyclic aromatic hydrocarbons (PAHs) were obtained. The grafting of α-phenolate groups on the phosphorus center enhances the coplanarity of the system.

1-Phosphafulvenes can be easily generated by dissociation of dimers resulting from the reaction of phospholes with aldimines. As electron-rich partners, they act as 4π phosphadienic systems toward alkenes and alkynes in [4 + 2] cycloaddition reactions. As electron-poor partners, they act either as 2π systems toward conjugated dienes in [2 + 4] cycloaddition reactions via their P═C double bond or as 6π systems toward phosphadienes in [6 + 4] cycloaddition reactions.

Under Pd(II)/CuI cocatalysis, o-diarylphosphinophenylalkynes cyclize in boiling toluene via C-P bond cleavage and arylphosphination of the C≡C bond. This protocol provides an unprecedented atom- and step-efficient access to optoelectronically and biologically interesting benzophospholes.

Phospholes react with aldimines at 170 °C in the presence of mild Lewis acids to give C2-bridged biphospholes in good yields. The mechanism includes a series of [1,5] shifts of the P-substituents around the phosphole ring, a P-H + aldimine condensation, and the formation of a transient three-membered ring that dimerizes.

Phospholides are easily obtained by treatment of the open-chain acetylenic phosphines shown by an excess of lithium at room temperature in THF (12 examples).

Herein, a Pd-catalyzed reaction of simple and diverse bromothiophenes with alkynes via regioselective C-S bond activation is reported. This provides a new approach to prepare sulfur-based heterocycles and fulvenes., (© 2011 American Chemical Society)

A series of chiral 3-aryl-4-phosphonobutyric acid esters were synthesized in high enantioselectivities (93-98% ee) via the Rh-catalyzed asymmetric hydrogenation of the corresponding 3-aryl-4-phosphonobutenoates using a P-stereogenic BoPhoz-type phosphine-aminophosphine ligand. The methodology has been successfully applied to the asymmetric synthesis of a potential GABA(B) antagonist, (R)-phaclofen, in high enantioselectivity.

An enantioselective synthesis of chiral alkylphosphonates bearing a beta-stereogenic center, based on the Rh-catalyzed asymmetric hydrogenation of corresponding beta-substituted beta,gamma-unsaturated phosphonates with a ferrocene-based monophosphoramidite ligand under the mild hydrogenation conditions, was developed, in which an ee value of up to 98% was obtained.

The hydrolysis of a phosphanorbornenium triflate gives the expected tertiary phosphine oxide by cleavage of one P-C bond of the bridge in the presence of triethylamine but affords the secondary phosphine oxide by cleavage of the two P-C bonds of the bridge in the presence of alpha-picoline.

A new class of chiral ferrocenyl diphosphine ligands with an imidazole ring, (R(c),S(Fc))-ImiFerroPhos, has been prepared from acylferrocenes through a five-step transformation and successfully applied in the Rh-catalyzed asymmetric hydrogenation of various 3-aryl-substituted 2-phosphonomethylpropenoates, in which a series of chiral 3-phosphono-2-arylmethylpropanoic acid derivatives were achieved in ee values of up to 98%.

An enantioselective synthesis of optically active 1-aryl or 1-alkyl substituted ethylphosphonates, based on the first Rh-catalyzed asymmetric hydrogenation of corresponding alpha,beta-unsaturated precursors with a P-stereogenic BoPhoz-type ligand under the mild condition, was developed, in which a wide range of 1-aryl or 1-alkyl substituted ethylphosphonates were achieved in up to 98% ee.

A series of chiral beta-aryl-substituted gamma-amino butyric acid derivatives were synthesized in good enantioselectivities via the Cu-catalyzed asymmetric conjugate reduction of gamma-phthalimido-alpha,beta-unsaturated carboxylic acid esters using Cu(OAc)2 x H2O as a catalyst precursor, (S)-BINAP as a ligand, PMHS as a hydride source, and t-BuOH as an additive. The methodology has been applied successfully to the enantioselective synthesis of a chiral pharmaceutical, (R)-baclofen.

A new class of unsymmetrical hybrid phosphine--aminophosphine ligands has been prepared from commercially available, inexpensive (S)-1-phenylethylamine through a concise synthetic procedure. These ligands are not very sensitive to air and moisture, and displayed good enantioselectivities in the Rh-catalyzed asymmetric hydrogenation of various dimethyl alpha-benzoyloxyethenephosphonates bearing beta-aryl, beta-alkyl, and beta-alkoxy substituents and N-benzyloxycarbonyl alpha-enamido phosphonates, in which up to 97% ee was obtained. A side-by-side comparison study disclosed that these new phosphine--aminophosphine ligands showed better enantioselectivity than BoPhoz ligands.

A series of BoPhoz-type ligands were successfully applied in the rhodium-catalyzed asymmetric hydrogenation of a number of beta-substituted or unsubstituted alpha-(phthalimidomethyl)acrylates, affording good to excellent enantioselectivities. The results suggested that the presence of an N-H proton in the BoPhoz backbone could significantly improve the enantioselectivity, and ligand (Sc,Rp)-1d, bearing two CF3-groups in the 3,5-position of the phenyl ring of aminophosphino moiety, showed the highest enantioselectivity.

The one-pot, palladium-catalyzed, three-component coupling of aryl bromides, internal alkynes, and environmentally friendly K4[Fe(CN)6] provides an efficient and direct method for the preparation of beta-arylalkenylnitriles.