Enantioselective Copper-Catalyzed Alkynylation of Benzylic C-H Bonds via Radical Relay.
Fu, Liang; Zhang, Zhihan; Chen, Pinhong; Lin, Zhenyang; Liu, Guosheng; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c05373

data_4135096
_publ_section_title
;
 Enantioselective Copper-Catalyzed Alkynylation of Benzylic C-H Bonds via
 Radical Relay.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c05373
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_sum            'C22 H20 N4 O3 S'
_chemical_formula_weight         420.48
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           SHELXL-2013
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.7177(4)
_cell_length_b                   10.0431(5)
_cell_length_c                   22.0386(10)
_cell_measurement_reflns_used    7639
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      52.451
_cell_measurement_theta_min      4.457
_cell_volume                     2150.88(17)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_structure_solution    'SHELXS-97 (Sheldrick 2008)'
_diffrn_ambient_temperature      296(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0473
_diffrn_reflns_av_unetI/netI     0.0368
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            19750
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.998
_diffrn_reflns_theta_min         2.290
_exptl_absorpt_coefficient_mu    0.181
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6291
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   sadabs
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.298
_exptl_crystal_description       prismatic
_exptl_crystal_F_000             880
_exptl_crystal_size_max          0.180
_exptl_crystal_size_mid          0.110
_exptl_crystal_size_min          0.070
_refine_diff_density_max         0.246
_refine_diff_density_min         -0.235
_refine_diff_density_rms         0.073
_refine_ls_abs_structure_details
; 
 Flack x determined using 1340 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons and Flack (2004), Acta Cryst. A60, s61). 
;
_refine_ls_abs_structure_Flack   0.06(4)
_refine_ls_extinction_coef       0.030(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     274
_refine_ls_number_reflns         4215
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0559
_refine_ls_R_factor_gt           0.0431
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0609P)^2^+0.1173P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1017
_refine_ls_wR_factor_ref         0.1118
_reflns_Friedel_coverage         0.749
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                3548
_reflns_number_total             4215
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c05373_si_005.cif
_cod_data_source_block           mo_d8v18878_0m
_cod_database_code               4135096
_shelx_estimated_absorpt_t_min   0.968
_shelx_estimated_absorpt_t_max   0.987
_shelxl_version_number           2013-4
_shelx_res_checksum              32442
_shelx_hkl_checksum              53532