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_4135095
_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 rmad
_chemical_formula_moiety         'C20 H23 Br Si'
_chemical_formula_sum            'C20 H23 Br Si'
_chemical_formula_weight         371.38
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-07-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 98.177(9)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.2063(10)
_cell_length_b                   8.2335(13)
_cell_length_c                   18.476(3)
_cell_measurement_reflns_used    7659
_cell_measurement_temperature    170(2)
_cell_measurement_theta_max      55.29
_cell_measurement_theta_min      4.207
_cell_volume                     934.5(3)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      170.01
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.1262
_diffrn_reflns_av_unetI/netI     0.1428
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            8682
_diffrn_reflns_point_group_measured_fraction_full 0.960
_diffrn_reflns_point_group_measured_fraction_max 0.947
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         55.424
_diffrn_reflns_theta_min         4.206
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.416
_exptl_absorpt_correction_T_max  0.7508
_exptl_absorpt_correction_T_min  0.3477
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1715 before and 0.1172 after correction. The Ratio of minimum to maximum transmission is 0.4643. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.320
_exptl_crystal_description       plate
_exptl_crystal_F_000             384
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.005
_refine_diff_density_max         1.062
_refine_diff_density_min         -0.743
_refine_diff_density_rms         0.115
_refine_ls_abs_structure_details
;
 Flack x determined using 790 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.122
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     202
_refine_ls_number_reflns         3429
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.122
_refine_ls_R_factor_all          0.1007
_refine_ls_R_factor_gt           0.0841
_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^)+(0.1028P)^2^+0.0438P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2090
_refine_ls_wR_factor_ref         0.2314
_reflns_Friedel_coverage         0.803
_reflns_Friedel_fraction_full    0.932
_reflns_Friedel_fraction_max     0.911
_reflns_number_gt                2612
_reflns_number_total             3429
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c05373_si_003.cif
_cod_data_source_block           mj19476_0m
_cod_database_code               4135095
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.988
_shelx_estimated_absorpt_t_min   0.794
_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.a Ternary CH refined with riding coordinates:
 C1(H1)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C10(H10), C11(H11), C13(H13), C14(H14), C15(H15), C16(H16),
 C17(H17)
2.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              69597
_shelx_hkl_checksum              52273
_olex2_submission_special_instructions 'No special instructions were received'