# Electronic Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2011 data_global _journal_name_full Chem.Commun. _journal_coden_cambridge 0182 _journal_year ? _journal_volume ? _journal_page_first ? loop_ _publ_author_name _publ_author_address 'Hikaru Yanai' ; School of Pharmacy, Tokyo University of Pharmacy and Life Sciences 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan ; 'Masaya Fujita' '' 'Takeo Taguchi' '' _publ_contact_author_address ; School of Pharmacy, Tokyo University of Pharmacy and Life Sciences 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan ; _publ_contact_author_email yanai@toyaku.ac.jp _publ_contact_author_fax ? _publ_contact_author_phone ? # SUBMISSION DETAILS _publ_contact_author_name 'Hikaru Yanai' _publ_contact_letter ; ? ; _publ_requested_category ? _publ_section_title ; A regioselective synthesis of poly-substituted aryl triflones through self-promoting three component reaction ; data_CBA06-3af _database_code_depnum_ccdc_archive 'CCDC 821320' #TrackingRef 'CBA06-3af.cif' #============================================================================== # MF-183 #============================================================================== _audit_creation_date '30 Jul 2010' _audit_creation_method SHELXL-97 _publ_section_abstract ; In the absence of any additional catalysts, the reactions of (CF3SO)2CH2, aldehydes, and 1,3-dienes gave gem-bis(triflyl)cyclohexenes in excellent yields with highly regioselectivity. gem-Bis(triflyl)cyclohexene products can be easily converted to the corresponding aryl trifluoromethyl sulfones. ; _publ_section_comment ; ; #============================================================================== # TEXT #============================================================================== _publ_section_acknowledgements ; ; _publ_section_references ; Sheldrick, G. M. (1997). SHELXL97. Program for the Refinement of Crystal Structures. University of G\"ottingen, Germany. A.L.Spek (2004) PLATON, A Multipurpose Crystallographic Tool, Utrecht University, Utrecht, The Netherlands. or A.L.Spek, J.Appl.Cryst. 2003, 36, 7-13. ; #============================================================================== # CHEMICAL DATA #============================================================================== _chemical_name_systematic ; Ethyl 2-(6,6-bis(trifluoromethylsulfonyl)cyclohex-2-enyl)acetate ; _chemical_name_common ? _chemical_melting_point 89.0 _chemical_formula_moiety 'C12 H14 F6 O6 S2' _chemical_formula_sum 'C12 H14 F6 O6 S2' _chemical_formula_weight 432.35 _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_absolute_configuration . loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' #============================================================================== # CRYSTAL DATA #============================================================================== _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 21/c' _symmetry_space_group_name_Hall '-P 2ybc' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 8.1916(10) _cell_length_b 12.7099(16) _cell_length_c 16.097(2) _cell_angle_alpha 90.00 _cell_angle_beta 97.767(2) _cell_angle_gamma 90.00 _cell_volume 1660.5(4) _cell_formula_units_Z 4 _cell_measurement_temperature 90 _cell_measurement_reflns_used 4598 _cell_measurement_theta_min 2.51 _cell_measurement_theta_max 27.60 _exptl_crystal_description Block _exptl_crystal_colour Colorless _exptl_crystal_size_max 0.26 _exptl_crystal_size_mid 0.23 _exptl_crystal_size_min 0.17 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.729 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 880 _exptl_absorpt_coefficient_mu 0.413 _exptl_absorpt_correction_type analytical _exptl_absorpt_correction_T_min 0.9002 _exptl_absorpt_correction_T_max 0.9331 _exptl_absorpt_process_details ; Crystal Faces plugin in Bruker APEX2 software ; _exptl_special_details ; ? ; #============================================================================== # EXPERIMENTAL DATA #============================================================================== _diffrn_ambient_temperature 90 _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Bruker TXS fine-focus rotating anode' _diffrn_radiation_monochromator 'Bruker Helios multilayer confocal mirror' _diffrn_measurement_device_type 'Bruker APEXII CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean 8.333 _diffrn_reflns_number 9303 _diffrn_reflns_av_R_equivalents 0.0213 _diffrn_reflns_av_sigmaI/netI 0.0267 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 2.05 _diffrn_reflns_theta_max 27.64 _reflns_number_total 3765 _reflns_number_gt 3260 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'APEX2 (Bruker AXS, 2006)' _computing_cell_refinement 'APEX2 (Bruker AXS, 2006)' _computing_data_reduction 'SAINT (Bruker AXS, 2004)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'XSHEL (Bruker AXS,2002)' _computing_publication_material 'XCIF (Bruker AXS, 2001)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0339P)^2^+1.4602P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3765 _refine_ls_number_parameters 236 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0385 _refine_ls_R_factor_gt 0.0317 _refine_ls_wR_factor_ref 0.0798 _refine_ls_wR_factor_gt 0.0757 _refine_ls_goodness_of_fit_ref 1.000 _refine_ls_restrained_S_all 1.000 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group C1 C 0.67990(19) -0.04432(13) 0.32931(9) 0.0134(3) Uani 1 1 d . . . C2 C 0.8904(2) -0.17819(14) 0.22222(10) 0.0197(3) Uani 1 1 d . . . C3 C 0.81571(19) 0.12023(13) 0.41272(10) 0.0164(3) Uani 1 1 d . . . H3A H 0.9299 0.0949 0.4286 0.020 Uiso 1 1 calc R . . H3B H 0.8086 0.1535 0.3567 0.020 Uiso 1 1 calc R . . C4 C 0.6831(2) -0.21137(13) 0.41784(10) 0.0176(3) Uani 1 1 d . . . H4A H 0.6129 -0.2698 0.4330 0.021 Uiso 1 1 calc R . . H4B H 0.7835 -0.2420 0.3995 0.021 Uiso 1 1 calc R . . C5 C 0.3435(2) 0.00864(14) 0.24526(10) 0.0188(3) Uani 1 1 d . . . C6 C 0.69528(19) 0.02667(13) 0.40906(9) 0.0144(3) Uani 1 1 d . . . H6 H 0.5836 0.0577 0.4107 0.017 Uiso 1 1 calc R . . C7 C 0.58952(19) -0.14742(13) 0.34624(10) 0.0154(3) Uani 1 1 d . . . H7A H 0.4786 -0.1301 0.3603 0.019 Uiso 1 1 calc R . . H7B H 0.5752 -0.1907 0.2946 0.019 Uiso 1 1 calc R . . C8 C 0.7740(2) 0.20033(14) 0.47628(10) 0.0178(3) Uani 1 1 d . . . C9 C 0.7330(2) -0.03873(14) 0.48825(10) 0.0175(3) Uani 1 1 d . . . H9 H 0.7612 -0.0016 0.5394 0.021 Uiso 1 1 calc R . . C10 C 0.7302(2) -0.14252(14) 0.49262(10) 0.0186(3) Uani 1 1 d . . . H10 H 0.7594 -0.1749 0.5457 0.022 Uiso 1 1 calc R . . C11 C 0.7717(3) 0.44491(15) 0.50010(12) 0.0269(4) Uani 1 1 d . . . H11A H 0.8328 0.4679 0.4550 0.040 Uiso 1 1 calc R . . H11B H 0.7598 0.5041 0.5378 0.040 Uiso 1 1 calc R . . H11C H 0.6623 0.4200 0.4759 0.040 Uiso 1 1 calc R . . C12 C 0.8637(2) 0.35717(14) 0.54842(11) 0.0210(4) Uani 1 1 d . . . H12A H 0.9699 0.3839 0.5774 0.025 Uiso 1 1 calc R . . H12B H 0.7985 0.3305 0.5914 0.025 Uiso 1 1 calc R . . F1 F 0.91868(16) -0.14054(10) 0.14983(7) 0.0354(3) Uani 1 1 d . . . F2 F 1.01467(17) -0.23907(10) 0.25120(8) 0.0445(3) Uani 1 1 d . . . F3 F 0.75459(15) -0.23389(10) 0.21091(8) 0.0381(3) Uani 1 1 d . . . F4 F 0.30968(12) 0.03827(9) 0.31995(6) 0.0235(2) Uani 1 1 d . . . F5 F 0.26792(12) 0.07213(9) 0.18728(6) 0.0241(2) Uani 1 1 d . . . F6 F 0.29026(12) -0.08842(9) 0.22953(7) 0.0256(2) Uani 1 1 d . . . O1 O 0.59252(15) -0.03692(11) 0.16443(7) 0.0243(3) Uani 1 1 d . . . O2 O 0.59403(15) 0.13370(10) 0.24143(8) 0.0238(3) Uani 1 1 d . . . O3 O 0.93149(14) 0.02585(10) 0.25407(8) 0.0202(3) Uani 1 1 d . . . O4 O 0.99301(14) -0.09975(10) 0.37258(7) 0.0193(3) Uani 1 1 d . . . O5 O 0.64939(16) 0.20059(11) 0.50822(9) 0.0283(3) Uani 1 1 d . . . O6 O 0.89417(14) 0.27170(9) 0.49169(7) 0.0185(2) Uani 1 1 d . . . S1 S 0.56824(5) 0.02273(3) 0.23714(2) 0.01628(10) Uani 1 1 d . . . S2 S 0.88918(5) -0.06462(3) 0.29937(2) 0.01434(10) Uani 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 C1 0.0100(7) 0.0179(8) 0.0123(7) 0.0000(6) 0.0020(5) -0.0002(6) C2 0.0212(8) 0.0197(9) 0.0189(8) -0.0028(7) 0.0057(7) 0.0003(7) C3 0.0132(7) 0.0194(8) 0.0172(8) -0.0029(6) 0.0049(6) -0.0024(6) C4 0.0161(8) 0.0188(8) 0.0182(8) 0.0022(6) 0.0042(6) -0.0008(6) C5 0.0143(8) 0.0258(9) 0.0159(8) 0.0012(7) 0.0002(6) -0.0006(6) C6 0.0121(7) 0.0181(8) 0.0135(7) -0.0024(6) 0.0032(6) -0.0019(6) C7 0.0138(7) 0.0170(8) 0.0156(7) -0.0017(6) 0.0027(6) -0.0034(6) C8 0.0168(8) 0.0185(8) 0.0182(8) -0.0011(6) 0.0028(6) -0.0025(6) C9 0.0151(8) 0.0245(9) 0.0131(7) -0.0009(6) 0.0025(6) -0.0034(6) C10 0.0141(8) 0.0272(9) 0.0143(8) 0.0030(7) 0.0018(6) -0.0014(7) C11 0.0338(11) 0.0221(9) 0.0248(9) -0.0039(7) 0.0034(8) 0.0032(8) C12 0.0251(9) 0.0209(9) 0.0169(8) -0.0060(7) 0.0023(7) -0.0041(7) F1 0.0529(8) 0.0350(7) 0.0225(6) -0.0061(5) 0.0207(5) -0.0043(6) F2 0.0544(8) 0.0345(7) 0.0407(7) -0.0124(6) -0.0082(6) 0.0246(6) F3 0.0352(7) 0.0382(7) 0.0452(7) -0.0242(6) 0.0212(6) -0.0181(5) F4 0.0166(5) 0.0380(6) 0.0162(5) 0.0005(4) 0.0037(4) 0.0020(4) F5 0.0187(5) 0.0329(6) 0.0195(5) 0.0058(4) -0.0018(4) 0.0047(4) F6 0.0174(5) 0.0288(6) 0.0292(6) -0.0001(5) -0.0023(4) -0.0053(4) O1 0.0219(6) 0.0367(8) 0.0145(6) -0.0010(5) 0.0032(5) 0.0013(5) O2 0.0201(6) 0.0226(7) 0.0280(7) 0.0077(5) 0.0011(5) -0.0009(5) O3 0.0183(6) 0.0193(6) 0.0250(6) 0.0013(5) 0.0099(5) -0.0015(5) O4 0.0137(6) 0.0263(7) 0.0180(6) -0.0014(5) 0.0020(4) 0.0004(5) O5 0.0216(7) 0.0302(7) 0.0360(7) -0.0129(6) 0.0149(6) -0.0076(5) O6 0.0174(6) 0.0182(6) 0.0201(6) -0.0038(5) 0.0035(5) -0.0044(5) S1 0.01351(19) 0.0215(2) 0.01388(18) 0.00301(15) 0.00191(14) -0.00031(15) S2 0.01204(19) 0.0167(2) 0.01492(19) -0.00092(15) 0.00428(14) -0.00108(14) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag C1 C7 1.547(2) . ? C1 C6 1.560(2) . ? C1 S1 1.8431(16) . ? C1 S2 1.8604(15) . ? C2 F1 1.309(2) . ? C2 F3 1.311(2) . ? C2 F2 1.313(2) . ? C2 S2 1.9051(17) . ? C3 C8 1.515(2) . ? C3 C6 1.541(2) . ? C3 H3A 0.9900 . ? C3 H3B 0.9900 . ? C4 C10 1.496(2) . ? C4 C7 1.529(2) . ? C4 H4A 0.9900 . ? C4 H4B 0.9900 . ? C5 F5 1.323(2) . ? C5 F6 1.321(2) . ? C5 F4 1.3244(19) . ? C5 S1 1.8720(17) . ? C6 C9 1.518(2) . ? C6 H6 1.0000 . ? C7 H7A 0.9900 . ? C7 H7B 0.9900 . ? C8 O5 1.203(2) . ? C8 O6 1.337(2) . ? C9 C10 1.321(2) . ? C9 H9 0.9500 . ? C10 H10 0.9500 . ? C11 C12 1.503(3) . ? C11 H11A 0.9800 . ? C11 H11B 0.9800 . ? C11 H11C 0.9800 . ? C12 O6 1.462(2) . ? C12 H12A 0.9900 . ? C12 H12B 0.9900 . ? O1 S1 1.4308(13) . ? O2 S1 1.4265(14) . ? O3 S2 1.4291(12) . ? O4 S2 1.4285(12) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C7 C1 C6 109.40(12) . . ? C7 C1 S1 109.65(11) . . ? C6 C1 S1 111.78(11) . . ? C7 C1 S2 114.07(11) . . ? C6 C1 S2 108.57(10) . . ? S1 C1 S2 103.30(7) . . ? F1 C2 F3 108.83(15) . . ? F1 C2 F2 108.04(15) . . ? F3 C2 F2 109.49(16) . . ? F1 C2 S2 108.70(12) . . ? F3 C2 S2 114.88(11) . . ? F2 C2 S2 106.68(12) . . ? C8 C3 C6 110.05(12) . . ? C8 C3 H3A 109.7 . . ? C6 C3 H3A 109.7 . . ? C8 C3 H3B 109.7 . . ? C6 C3 H3B 109.7 . . ? H3A C3 H3B 108.2 . . ? C10 C4 C7 110.12(14) . . ? C10 C4 H4A 109.6 . . ? C7 C4 H4A 109.6 . . ? C10 C4 H4B 109.6 . . ? C7 C4 H4B 109.6 . . ? H4A C4 H4B 108.2 . . ? F5 C5 F6 108.88(14) . . ? F5 C5 F4 109.38(14) . . ? F6 C5 F4 109.61(14) . . ? F5 C5 S1 105.26(11) . . ? F6 C5 S1 112.21(12) . . ? F4 C5 S1 111.37(11) . . ? C9 C6 C3 109.51(13) . . ? C9 C6 C1 111.04(13) . . ? C3 C6 C1 117.24(12) . . ? C9 C6 H6 106.1 . . ? C3 C6 H6 106.1 . . ? C1 C6 H6 106.1 . . ? C4 C7 C1 112.33(13) . . ? C4 C7 H7A 109.1 . . ? C1 C7 H7A 109.1 . . ? C4 C7 H7B 109.1 . . ? C1 C7 H7B 109.1 . . ? H7A C7 H7B 107.9 . . ? O5 C8 O6 124.37(16) . . ? O5 C8 C3 124.90(15) . . ? O6 C8 C3 110.72(13) . . ? C10 C9 C6 126.03(15) . . ? C10 C9 H9 117.0 . . ? C6 C9 H9 117.0 . . ? C9 C10 C4 123.07(15) . . ? C9 C10 H10 118.5 . . ? C4 C10 H10 118.5 . . ? C12 C11 H11A 109.5 . . ? C12 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? C12 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? O6 C12 C11 110.13(14) . . ? O6 C12 H12A 109.6 . . ? C11 C12 H12A 109.6 . . ? O6 C12 H12B 109.6 . . ? C11 C12 H12B 109.6 . . ? H12A C12 H12B 108.1 . . ? C8 O6 C12 115.88(13) . . ? O2 S1 O1 121.83(8) . . ? O2 S1 C1 111.35(8) . . ? O1 S1 C1 107.75(8) . . ? O2 S1 C5 103.40(8) . . ? O1 S1 C5 104.67(8) . . ? C1 S1 C5 106.58(7) . . ? O4 S2 O3 120.93(8) . . ? O4 S2 C1 107.25(7) . . ? O3 S2 C1 108.43(7) . . ? O4 S2 C2 104.24(8) . . ? O3 S2 C2 104.71(7) . . ? C1 S2 C2 111.11(7) . . ? _diffrn_measured_fraction_theta_max 0.976 _diffrn_reflns_theta_full 27.64 _diffrn_measured_fraction_theta_full 0.976 _refine_diff_density_max 0.647 _refine_diff_density_min -0.458 _refine_diff_density_rms 0.061