Supporting Information 1 H and 13C NMR spectra .............................................................................. S2-S26 S1 1H and 13C NMR spectra: 4-Methoxybiphenyl (3a) : S2 3-Methoxybiphenyl (3b): S3 2-Methoxybiphenyl (3c): S4 4-Methylbiphenyl (3d): S5 3-Methylbiphenyl (3e): S6 2-Methylbiphenyl (3f): S7 Biphenyl (3g): S8 4-Cyanobiphenyl (3h): S9 2-Cyanobiphenyl (3i): S10 1-Phenylnaphthalene (3j): S11 2-phenylpyridine (3k): S12 3-phenylpyridine (3l): S13 4-Fluorobiphenyl (3m): S14 4-Chlorobiphenyl (3n): S15 p-Terphenyl (3o): S16 4-Bromobiphenyl (3p): S17 3, 5-Dimethylbiphenyl (3q) : S18 3, 4-Dimethylbiphenyl (3r) : S19 2, 4-Dimethoxybiphenyl (3s): S20 2-(4-methoxyphenyl)pyrazine(3t): S21 Mixture of 4-methoxy-[1,1';4',1'']terphenyl, 4-methoxy-[1,1';3',1'']terphenyl (3u) : Mixture of 4-methoxy-2'-phenoxybiphenyl, 4-methoxy-3'-phenoxybiphenyl, 4-methoxy-4'-phenoxybiphenyl (3v): S22 Mixture of 4'-methoxybiphenyl-2-carbonitrile, 4'-methoxybiphenyl-3-carbonitrile, 4'-methoxybiphenyl-4-carbonitrile (3w): 2-(4-methoxyphenyl)pyridine (3x-o): S23 3-(4-methoxyphenyl)pyridine (3x-m): S24 4-(4-methoxyphenyl)pyridine (3x-p): S25 Mixture of 4', 5-dimethoxy-2-fluorobiphenyl, 2, 4'-dimethoxy-5-fluorobiphenyl (3y): S26 1 Sun CL, Li H, Yu DG, Yu M, Zhou X, Lu XY, Huang K, Zheng SF, Li BJ, Shi ZJ. An efficient organocatalytic method for constructing biaryls through aromatic C–H activation. Nat Chem, 2010, 2: 1044-1049 2 Shu ZB, Ye YX, Deng YF, Zhang Y, Wang JB. Palladium(II)-catalyzed direct conversion of methyl arenes into aromatic nitriles. Angew Chem Int Ed, 2013, 52: 10573-10576 3 Budén ME, Guastavino JF, Rossi RA. Room-temperature photoinduced direct C–H–arylation via base-promoted homolytic aromatic substitution. Org Lett, 2013, 15: 1174-1177 4 Qiu Y, Liu Y, Yang K, Hong W, Li Z, Wang Z, Yao Z, Jiang S. New ligands that promote cross-coupling reactions between aryl halides and unactivated arenes. Org Lett, 2011, 13: 3556-3559 5 Liu W, Cao H, Xin J, Lei AW. Cobalt-catalyzed direct arylation of unactivated arenes with aryl halides. Chem Eur J, 2011, 17: 3588-3592 6 Liu W, Cao H, Lei AW. Iron-catalyzed direct arylation of unactivated arenes with aryl halides. Angew Chem Int Ed, 2010, 49: 2004-2008 7 Wen J, Zhang J, Chen SY, Li J, Yu XQ. Iron-mediated direct arylation of unactivated arenes. Angew Chem Int Ed, 2008, 47: 8897-8900 8 Cheng YN, Gu XY, Li PX. Visible-light photoredox in homolytic aromatic substitution: direct arylation of arenes with aryl halides. Org Lett, 2013, 15: 2664-2667 9 Li PH, Wang L, Zhang L, Wang GW. Magnetic nanoparticles-supported palladium: a highly efficient and reusable catalyst for the Suzuki, Sonogashira, and Heck reactions. Adv Synth Catal, 2012, 354: 1307-1318 10 Tanimoro T, Ueno M, Takeda K, Kirihata M, Tanimori S. Proline catalyzes direct C–H arylations of unactivated arenes. J Org Chem, 2012, 77: 7844-7849 11 Beaumard F, Dauban P, Dodd RH. One-pot double Suzuki-Miyaura couplings: rapid access to nonsymmetrical tri(hetero)aryl derivatives. Org Lett, 2009, 11: 1801-1804 12 Ho JH, Lin YC, Chou LT, Chen YZ, Liu WQ, Chuang CL. Syntheses of p-terphenyls and 11,12-dihydroindeno[2,1-a]fluorene by one-pot benzannulation of Diels-Alder reactions of trans-1,2-dichloroethene and dienes. Tetrahedron Lett, 2013, 54: 1991-1993 13 Roman G, Christian MF. Negishi cross-coupling reactions catalyzed by an aminophosphine-based nickel system: a reliable and general applicable reaction protocol for the high-yielding synthesis of biaryls. Chem Eur J, 2011, 17: 11893-11904 14 (a) Shen T, Wang T, Qin C, Jiao N. Silver-catalyzed nitrogenation of alkynes: a direct approach to nitriles through C identical with C bond cleavage. Angew Chem Int Ed, 2013, 52: 6677-6680; (b) Chow WK, So CM, Lau CP, Kwong FY. Palladium-catalyzed borylation of aryl mesylates and tosylates and their applications in one-pot sequential Suzuki-Miyaura biaryl synthesis. Chem Eur J, 2011, 17: 6913-6917; (c) Zhou C, Liu QJ, Li YM, Zhang R, Fu XM, Duan CY. Palladium-catalyzed desulfitative arylation by C–O bond cleavage of aryl triflates with sodium arylsulfinates J Org Chem, 2012, 77: 10468-10472 15 Zhao HQ, Shen J, Guo JJ, Ye RJ, Zeng HQ. A macrocyclic aromatic pyridone pentamer as a highly efficient organocatalyst for the direct arylations of unactivated arenes. Chem Commun, 2013, 49: 2323-2325 S27