Synlett 2018; 29(19): 2547-2551
DOI: 10.1055/s-0037-1610261
cluster
© Georg Thieme Verlag Stuttgart · New York

Iterative Synthesis of Edge-Bent [3]Naphthylene

Zexin Jin
a  Department of Chemistry, Stanford University, Stanford, California 94305, United States   Email: yanx@stanford.edu
,
Yew Chin Teo
a  Department of Chemistry, Stanford University, Stanford, California 94305, United States   Email: yanx@stanford.edu
,
Simon J. Teat
b  Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
,
Yan Xia  *
a  Department of Chemistry, Stanford University, Stanford, California 94305, United States   Email: yanx@stanford.edu
› Author Affiliations
This work was supported by a Cottrell Scholar Award (24067) from the Research Corporation for Science Advancement.
Further Information

Publication History

Received: 22 June 2018

Accepted after revision: 15 July 2018

Publication Date:
28 August 2018 (eFirst)

Published as part of the Cluster Synthesis of Materials

Abstract

Polycyclic conjugated hydrocarbons (PCHs) containing antiaromatic rings are of fundamental and technical interest. [N]naphthylene is an intriguing family of PCHs consisting of alternatingly fused naphthalenoids and antiaromatic cyclobutadienoids (CBDs). We recently reported the first three regioisomers of the [N]naphthylene family, synthesized by catalytic arene-norbornene annulation (CANAL) reaction followed by acidic aromatization. We now report an iterative strategy for CANAL synthesis allowing us to synthesize the forth regioisomer, edge-bent [3]naphthylene. The optoelectronic properties, local paratropicity, and crystal packing of the edge-bent [3]naphthylene were studied and compared with its closely related regioisomer, center-bent [3]naphthylene.

Supporting Information

 
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  • 13 Compound 10 To an oven-dried 15 mL pressure tube was added 8 (56.8 mg, 0.132 mmol), 9 (74.5 mg, 0.14 mmol), palladium acetate (2.9 mg, 0.013 mmol) and Johnphos ligand (7.7 mg, 0.026 mmol). The tube was then transferred to a glovebox, and cesium carbonate (44.0 mg, 0.132 mmol) and THF (1mL) were added. The tube was closed and taken outside glovebox. The mixture was stirred at room temperature for 5 min, and then heated to 130 °C. After 24 h, the reaction was cooled to room temperature, and was passed through a thin layer of Celite to remove the inorganic salt. The solution was concentrated in vacuo and the residue was purified by column chromatography (1:10 EtOAc/hexanes) to yield 10 as a light yellow solid (70.5 mg, 66% yield). 1H NMR (400 MHz, chloroform-d): δ = 7.85 (d, J = 8.4 Hz, 1 H), 7.68 (d, J = 8.3 Hz, 1 H), 7.53 (d, J = 7.9 Hz, 1 H), 7.45 – 7.35 (m, 2 H), 7.34 (s, 1H), 7.33 (s, 2 H), 7.30 (ddd, J = 8.1, 6.7, 1.1 Hz, 1 H), 7.21 (d, J = 7.9 Hz, 1 H), 3.47 (s, 2 H), 2.58 (s, 3 H), 2.36 (s, 3 H), 1.85 (s, 3 H), 1.84 (s, 3 H), 1.17 (s, 42 H) ppm. 13C NMR (101 MHz, chloroform-d): δ = 148.53, 148.21, 147.46, 144.50, 143.83, 140.59, 140.48, 137.17, 137.05, 134.74, 130.03, 129.77, 127.12, 126.36, 125.41, 124.36, 124.28, 123.27, 119.59, 119.48, 118.40, 118.12, 117.81, 105.78, 94.82, 83.87, 55.11, 55.09, 18.80, 16.44, 14.95, 14.22, 11.36 ppm. m/z [M + Na+] calcd for C56H66OSi2: 833.46; found: 833.45.
  • 14 [3]Naphthylene 1 Compound 10 (20.0 mg, 0.022 mmol) was dissolved in isopropyl alcohol (1 mL), chloroform (0.5 mL), and HCl (0.2 ml, 37%). The solution was heated at 80 °C for 24 h. The reaction mixture was cooled, and the aromatized product had crushed out of the solution. The product 1 was collected by filtration and washed with MeOH to give an orange solid (15.8 mg, 82%). 1H NMR (500 MHz, chloroform-d): δ = 7.67 (d, J = 8.4 Hz, 1 H), 7.59 (d, J = 8.3 Hz, 1 H), 7.55 (s, 1 H), 7.54 (s, 1 H), 7.40 (d, J = 7.8 Hz, 1 H), 7.34 (t, J = 7.5 Hz, 1 H), 7.24 (t, J = 7.6 Hz, 1 H), 7.07 (d, J = 7.9 Hz, 1 H), 7.05 (s, 1 H), 7.03 (s, 1 H), 2.46 (s, 3 H), 2.35 (s, 3 H), 2.34 (s, 3 H), 2.28 (s, 3 H), 1.19 (s, 42 H) ppm. 13C NMR (101 MHz, chloroform-d): δ = 148.33, 147.35, 146.34, 146.20, 146.10, 145.52, 145.51, 145.44, 137.73, 137.64, 134.94, 134.92, 134.71, 130.23, 129.76, 129.49, 129.46, 127.13, 125.98, 125.63, 124.02, 121.85, 121.80, 120.23, 120.19, 120.00, 117.19, 114.64, 114.22, 106.66, 93.90, 19.10, 16.55, 15.13, 14.71, 14.64, 11.70 ppm. m/z [M + Na+] calcd for C56H64Si2: 815.44; found: 815.34.