Kazunobu Igawa

Directing group-controlled hydrosilylation: Regioselective functionalization of alkyne

Pt(0)-catalyzed hydrosilylation of unsymmetric alkynes proceeds in a highly regioselective manner with a dimethylvinylsilyl (DMVS) group as the directing group. This hydrosilylation affords a single regioisomer of silylalkenes from propargylic and homopropargylic alcohol derivatives. DMVS also has an accelerating effect that allows group-selective hydrosilylation of the DMVS-attached alkyne prior to that of other alkynes. Combined hydrosilylation and transformation reactions of the resulting silylalkenes afford various tri-substituted alkenes and multi-oxy-functionalized compounds with high regioselectivity from unsymmetric alkynes.

Enantioselective Synthesis of Silanol

An enantioselective nucleophilic substitution reaction of achiral dialkoxysilane has been developed. The reaction proceeds with efficient stereocontrol on the silicon chirality center to give the enantioenriched silyl ether, which can be converted to the silanol without loss of enantiopurity. We have analyzed the steric course of the reaction by using DFT calculations and propose a transition state model to explain the observed enantioselectivity.

Preparation and investigation of the formation mechanism of submicron-sized spherical particles of gold using laser ablation and laser irradiation in liquids.

Results of very recent studies have shown that laser irradiation (LI) of colloidal nanoparticles (NPs) using a non-focused laser beam at moderate fluence transforms the NPs to submicron-sized spherical particles (SMPs). For this study, we applied this technique to prepare gold SMPs from source gold NPs prepared by laser ablation of a gold plate in an aqueous solution. Results show that SMPs were obtained from NPs in pure water, but a considerably large amount of the source NPs were sedimented without LI. On the other hand, SMPs were not obtained from NPs stabilized by 1 mM citrate. These findings indicate that the agglomeration of the source NPs prior to the laser-induced melting is important to obtain SMPs, although the sedimentation of the source NPs caused by considerable agglomeration should be reduced to obtain SMPs efficiently. A proper condition of the agglomeration tendency of the source NPs to prepare SMPs reducing the sedimentation of the source NPs was obtainable by simply adjusting the citrate solution concentration. Moreover, investigation of the temporal dynamics of the formation process of SMPs suggested that the agglomeration of the source NPs not only is controlled by citrate but also is induced by LI. LI brings about the decomposition and removal of citrate molecules on the surface of the source NPs, and cause the agglomeration of the source NPs dynamically; then it brings about the fusion of the agglomerated NPs.

Direct Thioamination of Arynes via Reaction with Sulfilimines and Migratory N-Arylation

A novel method for preparing a diverse range of o-sulfanylanilines is described. Direct thioamination of arynes with sulfilimines gives o-sulfanylanilines, involving C-N and C-S bond formations and migratory N-arylation.

Catalytic enantioselective synthesis of alkenylhydrosilanes

Nonracemic silanes possessing a silicon stereocenter have structural similarity to their carbon congeners, but show substantial differences in their physical and electronic properties. Therefore, nonracemic silanes have attracted attention in the fields of synthetic, material, and bioorganic chemistry. Despite their potential importance, nonracemic silanes are unavailable in nature, and therefore the development of an efficient asymmetric method for their preparation is eagerly awaited. Among the several possible methods for the asymmetric synthesis of chiral silanes, desymmetrization of achiral silanes A would be the most rational approach (Scheme 1). Previously, we had developed asymmetric syn-

Highly Twisted N,N-Dialkylamines as a Design Strategy to Tune Simple Aromatic Hydrocarbons as Steric Environment-Sensitive Fluorophores

The steric-environment sensitivity of fluorescence of 9,10-bis(N,N-dialkylamino)anthracenes (BDAAs) was studied experimentally and theoretically. A new design strategy to tune simple aromatic hydrocarbons as efficient aggregation-induced emission (AIE) luminogens and molecular rotors is proposed. For a variety of BDAAs, prominent Stokes shifts and efficient solid-state fluorescence were observed. Calculations on BDAA-methyl suggested that in the ground state (S0) conformations, the pyramidal amine groups are highly twisted, so that their lone-pair orbitals cannot conjugate with the anthracene π orbitals. Fluorescence takes place from the S1 minima, in which one or both amine groups are planarized. The stability of the S1 excited state minima as well as destabilization of the S0 state is the origin of large Stokes shift. Experimental measurement of the nonadiabatic transition rate suggests that para disubstitution by dialkylamino (or strongly electron-donating) groups is a key for fast internal conversion. Minimum energy conical intersection (MECI) between S1 and S0 states was found to have a Dewar-benzene like structure. Although this can be reached efficiently in liquid phase for fast internal conversion, a large amplitude motion is required to reach this MECI, which is prohibited in the solid state and caused efficient AIE. This strategy is used to find experimentally that naphthalene analogues are also efficient AIE luminogens. The flexibility of alkyl chains on amino groups is also found to be important for allowed charge-transfer transition. Thus, three points [(1) highly twisted N,N-dialkylamines, (2) substitution at the para positions, (3) with flexible alkyl groups] were proposed for activation of small aromatic hydrocarbons.

Enantioselective synthesis of planar chiral organonitrogen cycles

Enantioselective synthesis of a planar chiral organonitrogen cycle has been newly developed based on the unprecedented prochiral face-selective cyclization of achiral linear precursors by an appropriate chiral promoter.

The effect of regioisomerism on the solid-state fluorescence of bis(piperidyl)anthracenes: structurally simple but bright AIE luminogens†

A series of regioisomers of piperidylanthracenes (PA) and bis(piperidyl)anthracenes (BPA) were synthesized and their photophysical properties examined in solution, suspension, and the solid state. Aggregation-induced emission (AIE) was observed only for 1,4-BPA and 9,10-BPA, in which two piperidyl groups are substituted at the anthracene moiety in the para-position with respect to each other. Compared to previously reported AIE luminogens, these easily obtainable para-substituted BPAs, exhibited several unique and beneficial features, such as simple structures, bright solid-state fluorescence (Φfl = 0.49 and 0.86 for 1,4-BPA and 9,10-BPA, respectively), tunable fluorescence emission, and large Stokes shifts. Results from diffuse-reflectance and fluorescence lifetime measurements demonstrated that PAs and BPAs intrinsically possess an efficient non-radiative transition pathway in the solid state, and that 1,4-BPA and 9,10-BPA may overcome this pathway. The X-ray crystallographic analysis of 1,4-BPA revealed that undesirable interchromophoric interactions can be minimised, while TD-DFT calculations suggested that the enhanced Stokes shift of 1,4-BPA arises from severe electronic repulsion between neighbouring piperidyl moieties, which presumably results in the absence of self-absorption.

Heteroatom‐embedded Medium‐Sized Cycloalkynes: Concise Synthesis, Structural Analysis, and Reactions

A variety of medium-sized cycloalkynes were efficiently synthesized by the double Nicholas reaction of cobalt complex and bis(hetero)substituted acyclic compound. The alkyne moiety within the ring has a unique bent structure and high reactivity toward cycloaddition reactions. Furthermore, preparation of multifunctionalized alkynes was achieved by embedding the cycloalkyne within a peptide chain.

Nucleophilic Substitution Reaction at the Nitrogen of Arylsulfonamides with Phosphide Anion

A novel nucleophilic substitution reaction at the nitrogen of arylsulfonamides by means of phosphide anions has been described. This reaction allows for the efficient transformation of arylsulfonamides into synthetically valuable phosphamides, amines, and a variety of protected amines.