1 Supporting Information-OL A Facile Synthesis of Complicated 9,9-Diarylfluorenes Based on BF 3 ⋅Et 2 O-mediated Friedel-Crafts Reaction Ling-Hai Xie, † Xiao-Ya Hou, † Yu-Ran Hua, † Chao Tang, † Feng Liu, † Qu-Li Fan, † and Wei Huang †,‡, * † Institute of Advanced Materials (IAM), Fudan University, 220 Handan Raod, Shanghai 200433, People’s Republic of China ‡ Faculty of Engineering, National University of Singapore, 9 Engineering Drive 1, Singapore 117576, Republic of Singapore Email: wei-huang@fudan.edu.cn; chehw@nus.edu.sg Experimental Section Chemicals: magnesium turnings, thiophene, fluorenone, carbazole, pyrene, tert-butylbenzene, phenyl ether and tetrakistriphenylphosphine palladium(0) were obtained from Aldrich Chemical Co. and were used without further purification. 3,3-bithiophene, biphenyl boronic acid, 9-phenyl-fluoren-9-ol, 1 2-bromo-9-phenyl-fluoren-9-ol, 1 and 2,7-dibromo-9-phenyl-fluoren-9-ol, 1 spiro[[8H]indeno[2,1-b]thiophene-8,9'-fluorene], 2 9-(3-phenylthiophene-2-yl)-9- {spiro[[8H]indeno[2,1-b]thiophene-8,9'-fluorene]-2-yl}fluorene, 2 and spiro[cyclopenta[1,2-b:4,3- b']dithiophene-7,9'-fluorene] 3 were prepared as previously reported. THF and diethyl ether were dried over sodium benzophenone ketyl anion radical and distilled under a dry nitrogen atmosphere immediately prior to use. All reactions involving organometallic reagents were carried out under nitrogen. Procedures: Melting points were determined by a Fukai (Beijing) X-4 digital melting point instrument. 1 H- and 13 C-NMR in CDCl 3 was recorded at 400 MHz using a Varian (1) Wong, K.-T.; Wang, Z.-J.; Chien, Y.-Y.; Wang, C.-L. Org. Lett. 2001, 3(15), 2285-2288. (2) Xie, L.-H.; Fu, T.; Hou, X.-Y.; Tang, C. Hua, Y.-R.; Wang, R.-J. Si, S.-M.; Fan, Q.-L.; Peng, B.; Wang, L.-H.; Wei, W.; Huang, W.. Tetrahedron Lett. Accepted. (3) Xie, L.-H.; Hou, X.-Y.; Fu, T.; Tang, C. Hua, Y.-R.; Wang, R.-J. Si, S.-M.; Fan, Q.-L.; Peng, B.; Wang, L.-H.; Wei, W.; Huang, W. Tetrahedron. submitted.