| 1. |
Takayuki Iwata∗ , Mizuki Hyodo , Takumi Fujiwara , Ryusei Kawano , Leah Kuhn , Igor V. Alabugin , Mitsuru Shindo, 3-Trifluoromethylbenzyne: Precise Orientation in Cycloaddition Reaction Enabled Regioselective Synthesis of Trifluoromethylated Triptycenes, Synthesis, 2022.04, The first regioselective addition reactions to 3-trifluoromethylbenzyne are reported. Triple cycloaddition of ynolates to the benzyne provided 1,8,13-tris(trifluoromethyl)triptycenes with high regioselectivity. 1-Trifluoromethyltriptycenes were regioselectively obtained by the Diels–Alder reaction of anthranoxides with the benzyne. These selectivities are attributed to the electron-acceptor nature of the trifluoromethyl group on the benzyne.. |
| 2. |
Mitsuru Shindo, Takayuki Iwata , Cycloaddition Initiated by Ynolates: High-Energy Dianion Equivalents as a Molecular Glue, Synlett , 10.1055/s-0040-1719857, 33, 06, 531-545, 2021.11, In this paper, ynolate-initiated cycloaddition (annulation) to form a range of carbocycles and heterocycles is described. Ynolates consist of a ketene anion equivalent, which contains both nucleophilic and electrophilic moieties, and a carbodianion equivalent that achieves double addition. Hence, in addition to the usual [n+2] cycloaddition, ynolates can perform formal [n+1]-type annulations. Their high-energy performance has been demonstrated by their triple addition to arynes to generate triptycenes, in which the C–C triple bond of ynolates is cleaved. The synthetic applications of these methods, including natural products synthesis, are also described.. |
| 3. |
T. Iwata, R. Kawano, T. Fukami, M. Shindo, Retro-Friedel-Crafts-Type Acidic Ring-Opening of Triptycenes: A New Synthetic Approach to Acenes, Chem. Euro. J., 10.1002/chem.202104160, 28, 12, e202104160, 2022.01, The triptycene scaffold has been ring-opened in a retro-Friedel-Crafts-type reaction under acidic conditions to give its corresponding anthrone product. 9-Hydroxytriptycenes and unsubstituted triptycene undergo ring-opening reaction under strongly acidic conditions, such as with TfOH. An investigation of the substitution effect has revealed that the electron-donating group on the arene moiety allows the reaction to proceed in the presence of a weaker acid, such as TFA. In addition, the reaction has been successfully applied toward the synthesis of tetracene.. |
| 4. |
T. Iwata, S. Kumagai, T. Yoshinaga, M. Hanada, Y. Shiota, K. Yoshizawa, M. Shindo, Quadruple Role of Pd Catalyst in Domino Reaction Involving Aryl to Alkyl 1,5-Pd Migration to Access 1,9-Bridged Triptycenes., Chem. Euro. J. accepted, 2021.06. |
| 5. |
T. Iwata, T. Yoshinaga, M. Shindo, Flow synthesis of triptycene via triple cycloaddition of ynolate to benzyne, Synlett、31, 1903-1906 (2020), 2020.07. |
| 6. |
S. Umezu, G. d. P. Gomes, T. Yoshinaga, M.Sakae, K. Matsumoto, T. Iwata, I. Alabugin, M. Shindo, Regioselective One-pot Synthesis of Triptycenes via Triple-Cycloadditions of Arynes to Ynolates, Angew. Chem. Int. Ed. 56, 1298-1302 (2017), 2016.12. |
