Palladium-Catalyzed Intramolecular Aminotrifluoromethoxylation of Alkenes.
Chen, Chaohuang; Chen, Pinhong; Liu, Guosheng; Journal of the American Chemical Society 137 (2015) 15648–15651; doi:10.1021/jacs.5b10971

data_4129846
_publ_section_title
;
 Palladium-Catalyzed Intramolecular Aminotrifluoromethoxylation of
 Alkenes.
;
_journal_issue                   50
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              15648
_journal_page_last               15651
_journal_paper_doi               10.1021/jacs.5b10971
_journal_volume                  137
_journal_year                    2015
_chemical_formula_moiety         'C25 H24 F3 N O3 S'
_chemical_formula_sum            'C25 H24 F3 N O3 S'
_chemical_formula_weight         475.51
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-06-08
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 102.985(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.9716(14)
_cell_length_b                   25.875(3)
_cell_length_c                   9.5523(13)
_cell_measurement_reflns_used    1562
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      19.14
_cell_measurement_theta_min      2.24
_cell_volume                     2401.6(5)
_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      296.15
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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  0.0673
_diffrn_reflns_av_unetI/netI     0.0688
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            17501
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         25.999
_diffrn_reflns_theta_min         1.574
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.184
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6682
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0599 before and 0.0470 after correction.
The Ratio of minimum to maximum transmission is 0.8962.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.315
_exptl_crystal_description       block
_exptl_crystal_F_000             992
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.799
_refine_diff_density_min         -0.580
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     299
_refine_ls_number_reflns         4704
_refine_ls_number_restraints     171
_refine_ls_restrained_S_all      1.209
_refine_ls_R_factor_all          0.1670
_refine_ls_R_factor_gt           0.0831
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1294P)^2^+2.5050P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2229
_refine_ls_wR_factor_ref         0.2876
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2207
_reflns_number_total             4704
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b10971_si_004.cif
_cod_data_source_block           dm15470
_cod_original_cell_volume        2401.6(6)
_cod_database_code               4129846
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.985
_shelx_estimated_absorpt_t_min   0.964
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 F2, C25, O1, C25
 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 O1 \\sim C25: within 2A with sigma of 0.005 and
sigma for terminal atoms of 0.01
C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01
C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17: within 2A with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(C19) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C22)
\\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(F2) \\sim Ueq,
Uanis(C25) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F3) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
4.a Ternary CH refined with riding coordinates:
 C2(H2)
4.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C3(H3A,H3B), C5(H5A,H5B)
4.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C13(H13), C14(H14), C15(H15),
 C16(H16), C17(H17), C19(H19), C20(H20), C22(H22), C23(H23)
4.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C)
;
_shelx_res_checksum              49560
_shelx_hkl_checksum              80664
_olex2_submission_special_instructions 'No special instructions were received'