The Preparation, Reactions, and Properties of Triphenylenes.

One-Pot Synthesis of Polysubstituted Spirofluorene–Indene via Ru(II)-Catalyzed [3 + 2] Annulation and Intramolecular Friedel–Crafts Cyclization

“…[1,1′-Biphenyl]-2-yl(4-methoxyphenyl)methanone (1a): white solid; 670 mg, 77% yield; 1 H NMR (400 MHz, CDCl 3 ) δ 7.65 (d,J = 8.8 Hz,2H),1H),3H),2H),3H),6.76 (d,J = 8.8 Hz,2H) (d,J = 8.4 Hz,2H),7.47 (d,J = 7.8 Hz,1H),7.42 (t,J = 7.8 Hz,1H),3H), 7.03 (t, J = 7.2 Hz, 1H), 6.89 (d,J = 8.4 Hz,2H),6.85 (d,J = 7.8 Hz,2H) (d,J = 7.8 Hz,2H),7.48 (d,J = 7.2 Hz,2 Hz),7.40 (t,J = 7.2 Hz,2H),3H),7.17 (t,J = 7.8 Hz,2H), 7.07 (d, J = 7.2 Hz, 2H), 6.98 (s, 1H), 6.89−6.87 (m, 1H), 6.81 (t, J = 7.8 Hz, 2H), 6.60− 6.55 (m, 4H), 3.78 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 159. 4, 147.2, 146.7, 146.5, 142.6, 142.2, 140.9, 135.3, 135.0, 129.6, 128.7, 128.6, 127.7, 127.7, 127.5, 127.4, 126.8, 123.7, 123.0, 120.2, 111.6, 106.8, 69.6, 55.5 4, 147.2, 146.7, 146.6, 146.4, 142.5, 142.2, 141.2, 139.6, 137.7, 135.4, 135.0, 129.7, 128.7, 128.7, 128.6, 127.6, 127.5, 127.4, 127.2, 126.8, 124.2, 123.6, 123.0, 119.9, 119.9, 111.6, 106.7, 69.4, 55.5, 21.7 (d,J = 8.4 Hz,2H), 7.49−7.47 (m, 2 H), 7.42−7.26 (m, 4H), 7.10 (t, J = 7.6 Hz, 1H), 7.03−7.01 (m, 1H), 6.98−6.97 (m, 1H), 6.90−6.87 (m, 2H), 6.82 (t, J = 7.6 Hz, 2H), 6.60−6.56 (m, 5H), 3.78 (s, 3H), 3.72 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 159.…”

“…4, 147.2, 146.7, 146.5, 142.6, 142.2, 140.9, 135.3, 135.0, 129.6, 128.7, 128.6, 127.7, 127.7, 127.5, 127.4, 126.8, 123.7, 123.0, 120.2, 111.6, 106.8, 69.6, 55.5 4, 147.2, 146.7, 146.6, 146.4, 142.5, 142.2, 141.2, 139.6, 137.7, 135.4, 135.0, 129.7, 128.7, 128.7, 128.6, 127.6, 127.5, 127.4, 127.2, 126.8, 124.2, 123.6, 123.0, 119.9, 119.9, 111.6, 106.7, 69.4, 55.5, 21.7 (d,J = 8.4 Hz,2H), 7.49−7.47 (m, 2 H), 7.42−7.26 (m, 4H), 7.10 (t, J = 7.6 Hz, 1H), 7.03−7.01 (m, 1H), 6.98−6.97 (m, 1H), 6.90−6.87 (m, 2H), 6.82 (t, J = 7.6 Hz, 2H), 6.60−6.56 (m, 5H), 3.78 (s, 3H), 3.72 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 159. 8, 159.4, 148.4, 147.2, 146.6, 146.0, 142.5, 142.1, 141.1, 135.3, 135.2, 135.0, 129.6, 128.7, 128.6, 127.6, 127.5, 127.5, 126.8, 126.6, 123.5, 123.0, 121.0, 119.4, 113.6, 111.6, 109.1, 106.8, 69.5, 55.5, 55.5 2-Fluoro-5′-methoxy-2′,3′-diphenylspiro[fluorene-9,1′-indene] (3da): white solid; 27.0 mg, 67% yield; 1 H NMR (400 MHz, CDCl 3 ) δ 7.71 (d,J = 7.6 Hz,1H),7.65 (d,J = 8.4 Hz,1H), 7.47−7.26 (m, 7H), 7.18 (t, J = 7.6 Hz, 1H), 7.07-6.89 (m, 4H), 6.82 (t, J = 7.6 Hz, 2H), 6.61−6.53 (m, 4H) 3.78 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 159. 6,147.4 (d,J CF = 205 Hz),146.6,146.4,143.0,141.0,140.7,140.0,135.0,134.7,133.3,129.6,128.7,128.6,128.1,128.0,127.9,127.7,127.6,126.9,123.9,123.7,123.0,121.1,120.3,111.8,107.0,69.4,…”

“…8, 159.4, 148.4, 147.2, 146.6, 146.0, 142.5, 142.1, 141.1, 135.3, 135.2, 135.0, 129.6, 128.7, 128.6, 127.6, 127.5, 127.5, 126.8, 126.6, 123.5, 123.0, 121.0, 119.4, 113.6, 111.6, 109.1, 106.8, 69.5, 55.5, 55.5 2-Fluoro-5′-methoxy-2′,3′-diphenylspiro[fluorene-9,1′-indene] (3da): white solid; 27.0 mg, 67% yield; 1 H NMR (400 MHz, CDCl 3 ) δ 7.71 (d,J = 7.6 Hz,1H),7.65 (d,J = 8.4 Hz,1H), 7.47−7.26 (m, 7H), 7.18 (t, J = 7.6 Hz, 1H), 7.07-6.89 (m, 4H), 6.82 (t, J = 7.6 Hz, 2H), 6.61−6.53 (m, 4H) 3.78 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 159. 6,147.4 (d,J CF = 205 Hz),146.6,146.4,143.0,141.0,140.7,140.0,135.0,134.7,133.3,129.6,128.7,128.6,128.1,128.0,127.9,127.7,127.6,126.9,123.9,123.7,123.0,121.1,120.3,111.8,107.0,69.4,55.5 (d,J = 8.0 Hz,1H),6H),2H),7.10 (d,J = 7.2 Hz,1H),6.99 (s,1H),1H),6.80 (t,J = 7.6 Hz,2H),1H),3H), 3.78 (s, 3H); 1...…”

“…The Journal of Organic Chemistry Article 3.78 (s, 3H), 3.16−3.10 (m, 2H), 1.40 (t, J = 7.6 Hz, 3H); 13 C NMR (100 MHz,CDCl 3 ) δ 159.3,147.5,146.8,146.7,146.7,142.7,142.4,141.3,139.6,139.5,135.4,135.0,129.6,128.7,128.6,128.0,127.6,127.6,127.5,127.4,127.0,126.7,123.6,123.4,122.9,121.2,111.6,106.7,69.4,55.5,27.1,14.2 (d,J = 7.6 Hz,1H),6H), 7.20 (t, J = 7.6 Hz, 1H), 7.14−6.97 (m, 4H), 6.93−6.81 (m, 4H), 6.61−6.59(m, 4H), 3.78 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 159. 6,158.4 (d,J CF = 250 Hz),149.4 (d,J CF = 5 Hz),146.6,146.6,145.9,142.8,140.3,139.3 (d,J CF = 3 Hz),135.1,134.8,129.6,129.3 (d,J CF = 15 Hz),128.9 (d,J CF = 7 Hz),128.7,…”

Gold-catalyzed cyclotrimerization of arynes for the synthesis of triphenylenes

“…To our knowledge, there are many methods for triphenylene formation via arynes. For examples, the cyclotrimerization of benzyne catalyzed by Cu(I) (20 mol%) afforded triphenylene in refluxing CH 3 CN (Scheme 1) [26], and triphenylenes were also isolated during attempts at obtaining a metal complex of arynes [27][28][29][30]. The efficient preparation of triphenylenes with a catalytic amount of promoters is still a demand to fulfill the modern synthesis.…”