Decoding the Mechanism of Intramolecular Cu-Directed Hydroxylation of sp(3) C-H Bonds.
Trammell, Rachel; See, Yi Yang; Herrmann, Aaron T.; Xie, Nan; Díaz, Daniel E; Siegler, Maxime A.; Baran, Phil S.; Garcia-Bosch, Isaac; The Journal of organic chemistry 82 (2017) 7887–7904; doi:10.1021/acs.joc.7b01069

data_4032633
_publ_section_title
;
 Decoding the Mechanism of Intramolecular Cu-Directed Hydroxylation of
 sp(3) C-H Bonds.
;
_journal_issue                   15
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              7887
_journal_page_last               7904
_journal_paper_doi               10.1021/acs.joc.7b01069
_journal_volume                  82
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C50 H68 Cu N4 O2, F6 P, 0.852(C3 H6 O)'
_chemical_formula_sum            'C52.56 H73.11 Cu F6 N4 O2.85 P'
_chemical_formula_weight         1015.10
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                90
_cell_angle_beta                 102.6341(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.91725(10)
_cell_length_b                   17.87891(15)
_cell_length_c                   22.3041(2)
_cell_measurement_reflns_used    35208
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      72.08
_cell_measurement_theta_min      3.14
_cell_volume                     5026.33(7)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_molecular_graphics    'SHELXTL v6.10 (Sheldrick, 2008)'
_computing_publication_material  'SHELXTL v6.10 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS-2014/7 (Sheldrick, 2015)'
_diffrn_ambient_temperature      110(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_source         'SuperNova (Cu) X-ray Source'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0302
_diffrn_reflns_av_unetI/netI     0.0284
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            61782
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         71.887
_diffrn_reflns_theta_min         2.030
_exptl_absorpt_coefficient_mu    1.486
_exptl_absorpt_correction_T_max  0.766
_exptl_absorpt_correction_T_min  0.653
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.341
_exptl_crystal_description       block
_exptl_crystal_F_000             2149
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.30
_exptl_crystal_size_min          0.22
_refine_diff_density_max         0.642
_refine_diff_density_min         -0.337
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 8502 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.011(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1320
_refine_ls_number_reflns         19559
_refine_ls_number_restraints     464
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0379
_refine_ls_R_factor_gt           0.0360
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0602P)^2^+1.0813P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0960
_refine_ls_wR_factor_ref         0.0979
_reflns_Friedel_coverage         0.920
_reflns_Friedel_fraction_full    0.989
_reflns_Friedel_fraction_max     0.983
_reflns_number_gt                18754
_reflns_number_total             19559
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b01069_si_004.cif
_cod_data_source_block           '[(S2)2CuI](PF6)'
_cod_depositor_comments
'Adding full bibliography for 4032630--4032633.cif.'
_cod_original_cell_volume        5026.32(7)
_cod_database_code               4032633
_shelx_shelxl_version_number     2014/7
_shelx_res_checksum              4462
_shelx_hkl_checksum              93759