Transforming Hetera‐Buckybowls into Chiral Conjugated Polycycles Incorporating Epoxycyclooctadiene: a Two‐Step Approach

• Published in: Chemistry : a European journal Vol. 29; no. 72; pp. e202303085 - n/a
• Main Authors: Wang, Xue, Hua, Xinqiang, Zhang, Haomin, Wu, Lingxi, Yuan, Chengshan, Liu, Zitong, Zhang, Hao‐Li, Shao, Xiangfeng
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 22.12.2023; Wiley Subscription Services, Inc
• Subjects: Benzene; cascade reaction; Chemistry; Chemistry, Multidisciplinary; Chiral π-conjugated polycycles; Hetera-buckybowls; Lithium; Magnesium; Magnesium bromides; metal ion-dependence; Metal ions; Nucleophiles; Optoelectronics; Physical Sciences; Quinones; Science & Technology; Synthesis; two-step synthesis; Hetera-buckybowls; HYDROCARBONS; cascade reaction; ALKYNYLPYRENES; RESOLUTION; two-step synthesis; ACTIVATED DELAYED FLUORESCENCE; TRICHALCOGENASUMANENE; SUMANENE; FUSED THIOPHENES; metal ion-dependence; Chiral pi-conjugated polycycles; DERIVATIVES; BOWL; DOUBLE HELICENE; Chiral π-conjugated polycycles
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202303085

Chiral π‐conjugated polycycles have garnered increasing attention due to versatile applications in optoelectronic materials and biological sciences. In this study, we report the synthesis of chiral π‐conjugated polycycles incorporating a chiral epoxycyclooctadiene moiety. Our synthetic strategy capitalizes on the novel reactions of hetera‐buckybowl triselenasumanene (TSS) and is achieved in two‐step manner. Firstly, the TSS is regio‐selectively transformed into its ortho‐quinone form. Subsequently, the nucleophilic addition reactions of TSS ortho‐quinone by phenylethynides are metal ion‐dependent. When utilizing (phenylethynyl)magnesium bromide as the nucleophile, two phenylethynyls are furnished onto the edged benzene ring of TSS. When the nucleophile is (phenylethynyl)lithium, a cascade of nucleophilic addition, intermolecular electron‐transfer, ring‐opening, and tetradehydro‐Diels–Alder (TDDA) reactions occur sequentially in one‐pot, ultimately affording chiral π‐conjugated polycycles featuring the epoxycyclooctadiene moiety as an integral part of their backbones. This work represents a step forward in the synthesis of chiral π‐conjugated polycycles using TSS as synthon. In this study, we present a novel approach to synthesize chiral π‐conjugated polycycles incorporating the epoxycyclooctadiene moiety, a key fragment found in the natural products. Our synthetic strategy capitalizes on innovative reactions involving hetera‐buckybowl triselenasumanene (TSS) and is achieved through a concise two‐step process.