Fig. 5: Scale-up reaction and product elaborations. | Nature Communications

Fig. 5: Scale-up reaction and product elaborations.

From: Asymmetric Büchner reaction and arene cyclopropanation via copper-catalyzed controllable cyclization of diynes

Fig. 5

a Preparative-scale reaction of 1a and synthetic applications. b Preparative-scale reaction of 3a and synthetic applications. Reagents and conditions: (i) Cu(MeCN)4PF6 (5 mol %), NaBArF4 (6 mol %), L9 (6 mol %), toluene, −20 °C, 9 d. (ii) Pd/C (10 mol %), H2 (1 atm), MeOH, rt, 12 h. (iii) Pd(OH)2/C (10 mol %), H2 (8 MPa), AcOH:EA = 1:1, 80 °C, 72 h. (iv) Cu(MeCN)4PF6 (10 mol %), NaBArF4 (12 mol %), L9 (12 mol %), DCM, 20 °C, 4 d. (v) Phenylacetylene (4 equiv), Pd(PPh3)4 (5 mol %), CuI (10 mol %), THF:Et3N = 3:1, 50 °C, 1 h. (vi) PhB(OH)2 (3.5 equiv), Pd(PPh3)4 (10 mol %), CsF (2.5 equiv), DME, 50 °C, 8 h. (vii) Cu(MeCN)4PF6 (5 mol %), NaBArF4 (6 mol %), L12 (6 mol %), 2-MeTHF, 0 °C, 51 h. (viii) KOH (10 equiv), THF:MeOH = 1:1, 50 °C, 1.5 h, then DMAP (20 mol %), (Boc)2O (3 equiv), Et3N (4 equiv), DCM, rt, 2 h. (ix) NaBH3CN (5 equiv), DCM:TFA = 10:1, rt, 1 h; Pd/C (10 mol %), H2 (1 atm), AcOH, 60 °C, 12 h. (x) DMAD (20 equiv), toluene, 60 °C, 12 h. (xi) MeOTf (10 equiv), Et2O, 0 °C to rt, 2 h; Pd(PPh3)2Cl2 (5 mol %), PhMgBr (2 equiv), THF, rt, 2 h.

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