Nonbenzenoid aromaticity of 1-phosphafulvenes: synthesis of phosphacymantrenes.

The coordination chemistry of 1-phosphafulvenes was investigated by employing their [6 + 4] adducts or α-C2-bridged biphospholes as a precursor. Unbridged phosphacymantrenes arise from 1-phosphafulvenes via proton abstraction. α-C2-bridged biphosphacymantrenes are probably yielded by the reductive coupling of 1-phosphafulvene with Mn2(CO)10. The coordination behavior of 1-phosphafulvenes is comparable to that of pentafulvenes, which again demonstrates the phosphorus-carbon analogy in low-coordinate organophosphorus chemistry.

Cleavage of the Inert C(sp2)-Ar σ-Bond of Alkenes by a Spatial Constrained Interaction with Phosphinidene.

[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(sp2)-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.

1,1-Addition of α-C2-Bridged Biphospholes with Alkynes.

An unusual chemoselective 1,1-addition of α-C2-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.

The chemistry of phosphirane-substituted phosphinidene complexes.

Thermolysis of the 1,1'-biphosphirane pentacarbonylmetal complex offers access to 3,4-dihydro-1,2-diphosphete and diphosphorus (P2) intermediates. A control reaction proves that this step-wise reaction is initiated by the dissociation of a W(CO)5 group. DFT calculations predict that further transformations proceed via a transient phosphiranylphosphinidene complex. The formation of the 3,4-dihydro-1,2-diphosphete derivative is thermodynamically favored, while a kinetic process provides the diphosphorus (P2) complex.

Copper(i)/Ganphos catalysis: enantioselective synthesis of diverse spirooxindoles using iminoesters and alkyl substituted methyleneindolinones.

A copper-catalyzed asymmetric 1,3-dipolar cycloaddition of glycine iminoesters with alkyl substituted 3-methylene-2-oxindoles is described. By using de novo design of P-stereogenic phosphines as ligands, spiro[pyrrolidin-3,3'-oxindole]s are generated in good to excellent yields with high asymmetric induction. A further reduced catalyst loading of 0.1 mol% is sufficient to achieve a satisfactory enantioselectivity of 90% ee. The DFT calculations suggest the second Michael addition of the 1,3-dipole to be the rate- and enantio-determining step. A key feature of this 1,3-dipolar cycloaddition is the wide substrate applicability, even with alkyl aldehyde-derived azomethine ylide; thus it has streamlined a highly enantioselective access to a new class of antiproliferative agents, MDM2-p53.

Enantioselective synthesis of indanone spiro-isochromanone derivatives via a dinuclear zinc-catalyzed Michael/transesterification tandem reaction.

An enantioselective Michael/transesterification tandem reaction of α-hydroxy indanones with ortho-ester chalcones was realized using dinuclear zinc catalysts. A series of enantiomerically pure spiro[indanone-2,3'-isochromane-1-one] derivatives were obtained in good yields with excellent stereoselectivities (up to >20 : 1 dr, up to >99% ee). This protocol could be conducted on a gram scale without affecting its stereoselectivities. In addition, the absolute stereochemistry of the products was determined by X-ray crystallographic analysis of 3ac, and a positive nonlinear effect was observed. Finally, a possible catalytic cycle was proposed to explain the origin of the enantioselectivity.

Concise Synthesis of Phospholene and Its P-Stereogenic Derivatives.

A simple method to build phospholene derivatives has been achieved in a one-pot reaction with readily available o-alkynylaryl bromides and alkylphosphine oxides. This method is also applicable to synthesize P-stereogenic phospholenes, and the resulting chiral phosphine was utilized as a ligand for coordination chemistry.

An Approach to Peri-Fused Heterocycles: A Metal-Mediated Cascade Carbonylative Cyclization/Dearomatic Diels-Alder Reaction.

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.

Transition-Metal-Like Reversible Cycloadditions of [tBuSP-W(CO)5 ] with Alkenes and Alkynes.

tert-Butylthiophosphinidene complex [tBuSP-W(CO)5 ] was generated by dissociation of 1-(tert-butylthio)phosphirane-W(CO)5 complex under mild conditions. The formation of transient [tBuSP-W(CO)5 ] was indicated by trapping reactions with 2,3-dimethyl-1,3-butadiene, alkynes, phenanthrene-9,10-dione, and methanol. The LUMO of [MeSP-W(CO)5 ] is significantly lower in energy than those of [Me2 NP-W(CO)5 ], [MeOP-W(CO)5 ], and [Me2 PP-W(CO)5 ]. The HOMO of [MeSP-W(CO)5 ] contains a significant contribution from the in-plane lone pair of P and the LUMO shows a typical π* characteristic. Since stabilized by sulfur lone pair and coordinated by W(CO)5 , [tBuSP-W(CO)5 ] undergoes facile and reversible cycloadditions with alkenes and alkynes.

Access to Chiral 2,5-Pyrrolidinyl Dispirooxindoles via Dinuclear Zinc-Catalyzed Asymmetric Cascade Reactions.

A series of new nonsymmetric semi-azacrown ether ligands were developed and applied to the asymmetric Michael/cyclic keto-imine formation/Friedel-Crafts alkylation reactions of 3-amino oxindole hydrochlorides and ß,γ-unsaturated α-keto amides. A diversity of 2,5-pyrrolidinyl dispirooxindoles containing two nonadjacent spiro-quaternary stereocenters were obtained in excellent diastereoselectivities and moderate to excellent enantioselectivities (up to 95% ee). A possible catalytic cycle was proposed to explain the origin of the asymmetric induction.

Ag/P-Stereogenic Phosphine-Catalyzed Enantioselective 1,3-Dipolar Cycloadditions: A Method to Optically Active Pyrrolidines.

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.

P-Stereogenic Phosphines Directed Copper(I)-Catalyzed Enantioselective 1,3-Dipolar Cycloadditions.

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.

An approach to 7-aza-1-phosphanorbornane complexes: strain promoted rearrangement of 1-iminylphosphirane complexes and cycloaddition with olefins.

1-Iminylphosphirane W(CO)5 complexes react with alkenes under an atmosphere of CO at 130 °C to form the original 7-aza-1-phosphanorbornane complexes. The reaction works well with both electron-rich and electron-poor alkenes. On the basis of DFT calculations, we propose a mechanism including the rearrangement of phosphirane into a dipolar five-membered ring and the following cycloaddition of this dipolar intermediate with alkenes.

Phosphindole fused pyrrolo[3,2-b]pyrroles: a new single-molecule junction for charge transport.

A new family of phosphindole fused ladder-type heteroacenes with a pyrrolo[3,2-b]pyrrole core were synthesized and characterized, which show good luminescence efficiency, high thermostability and tunable conductance.

Zwitterionic nido-Carborane-Fused Phospholes.

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.

Regioselective Synthesis of 2- or 2,7-Functionalized Pyrenes via Migration.

A simple method for the preparation of 2- or 2,7-functional pyrenes from 1- or 1,6-substituted derivatives is reported. The synthesis involves the unexpected 1,2-phosphinyl migration in an AlCl3/NaCl melt. The structure of the product has been unambiguously confirmed by X-ray crystallography. We also demonstrated that further functionalization of pyrene through C-P bond activation is possible. These 2,7-positions are difficult to derivatize otherwise.

The coordination chemistry of phosphinidene sulfides. Synthesis and catalytic properties of Pd4 and Pt4 clusters.

7-Phosphanorbornene sulfides were used as [RP = S] precursors. The reaction of these precursors with [M(PPh3)4] (M = Pd, Pt) yields star-like M4 clusters in which the central core is coated by three RP = S units acting as 4-electron µ2-P, η2-P = S ligands. The Pd cluster displays both stability and catalytic activity in the Suzuki-Miyaura reaction. DFT analysis suggests that a mononuclear [η2-RP = S]Pd(PPh3) complex is involved in the formation of the Pd4 clusters.

Synthesis of 1,3-Azaphospholes with Pyrrolo[1,2- a]quinoline Skeleton and Their Optical Applications.

A facile synthesis of 1,3-azaphospholes with a pyrrolo[1,2- a]quinoline skeleton has been described. These new annulated 1,3-azaphospholes exhibit good photoelectric performance and can be used as the emitting dopant in organic light-emitting diodes (OLEDs) and dye for bioimaging.

Selective Synthesis of (Z)-Diazadiphosphafulvalene from 2,2'-bis-Azaphosphindole.

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.

Planar Polycyclic Oxaphosphoranes Incorporating a Benzophosphole Unit.

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 σ5-oxaphosphoranes incorporating polycyclic aromatic hydrocarbons (PAHs) were obtained. The grafting of α-phenolate groups on the phosphorus center enhances the coplanarity of the system.