Copper(I)-Catalyzed Intramolecular Trifluoromethylation of Methylenecyclopropanes.
Zhu, Zi-Zhong; Chen, Kai; Yu, Liu-Zhu; Tang, Xiang-Ying; Shi, Min; Organic letters 17 (2015) 5994–5997; doi:10.1021/acs.orglett.5b02940

data_1555433
_publ_section_title
;
 Copper(I)-Catalyzed Intramolecular Trifluoromethylation of
 Methylenecyclopropanes.
;
_journal_issue                   24
_journal_name_full               'Organic letters'
_journal_page_first              5994
_journal_page_last               5997
_journal_paper_doi               10.1021/acs.orglett.5b02940
_journal_volume                  17
_journal_year                    2015
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C19 H18 F3 N O2 S'
_chemical_formula_sum            'C19 H18 F3 N O2 S'
_chemical_formula_weight         381.40
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yc'
_space_group_name_H-M_alt        'P 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-06-04
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.135(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.9711(12)
_cell_length_b                   9.9056(12)
_cell_length_c                   10.1296(13)
_cell_measurement_reflns_used    1830
_cell_measurement_temperature    130
_cell_measurement_theta_max      22.54
_cell_measurement_theta_min      2.276
_cell_volume                     897.8(2)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      130
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0258
_diffrn_reflns_av_unetI/netI     0.0384
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            6322
_diffrn_reflns_point_group_measured_fraction_full 0.861
_diffrn_reflns_point_group_measured_fraction_max 0.861
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         25.999
_diffrn_reflns_theta_min         2.056
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.223
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6729
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0518 before and 0.0446 after correction.
The Ratio of minimum to maximum transmission is 0.9019.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.411
_exptl_crystal_description       block
_exptl_crystal_F_000             396
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.970
_refine_diff_density_min         -0.523
_refine_diff_density_rms         0.091
_refine_ls_abs_structure_details
;
 Flack x determined using 969 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.03(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     236
_refine_ls_number_reflns         3047
_refine_ls_number_restraints     159
_refine_ls_restrained_S_all      1.156
_refine_ls_R_factor_all          0.0846
_refine_ls_R_factor_gt           0.0743
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1357P)^2^+0.9910P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1954
_refine_ls_wR_factor_ref         0.2090
_reflns_Friedel_coverage         0.730
_reflns_Friedel_fraction_full    0.729
_reflns_Friedel_fraction_max     0.729
_reflns_number_gt                2650
_reflns_number_total             3047
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol5b02940_si_001.cif
_cod_data_source_block           mo_dm15461_0m
_cod_database_code               1555433
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.957
_shelx_estimated_absorpt_t_min   0.946
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 F1, C12
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
3. Uiso/Uaniso restraints and constraints
F1 \\sim F2 \\sim F3 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7
\\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12: within 2A with sigma of 0.005
and sigma for terminal atoms of 0.01
Uanis(F1) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(F2) \\sim
Ueq, Uanis(C9) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C6)
\\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C3) \\sim Ueq: with
sigma of 0.005 and sigma for terminal atoms of 0.01
4.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C7(H7A,H7B), C8(H8A,H8B)
4.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C3(H3), C4(H4), C5(H5), C10(H10), C14(H14), C15(H15), C17(H17),
 C18(H18)
4.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C)
;
_shelx_res_checksum              56945
_shelx_hkl_checksum              52764
_olex2_submission_special_instructions 'No special instructions were received'