Nickel-catalyzed enantioselective α-heteroarylation of ketones via C–F bond activation to construct all-carbon quaternary stereocenters
Gu, Xiaodong; Liu, Kexin; Yang, Limin; Xie, Chengyi; Li, Mingliang; Wang, Jun (Joelle); Chemical Science 13 (2022) 12498–12502; doi:10.1039/D2SC03409C

data_1567817
_publ_section_title
;
 Nickel-catalyzed enantioselective \a-heteroarylation of ketones via C--F
 bond activation to construct all-carbon quaternary stereocenters
;
_journal_issue                   42
_journal_name_full               'Chemical Science'
_journal_page_first              12498
_journal_page_last               12502
_journal_paper_doi               10.1039/D2SC03409C
_journal_volume                  13
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H19 N O'
_chemical_formula_sum            'C25 H19 N O'
_chemical_formula_weight         349.41
_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             2021-06-30
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2022-03-07 deposited with the CCDC.	2022-09-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.4180(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.5649(3)
_cell_length_b                   10.4376(3)
_cell_length_c                   9.9968(3)
_cell_measurement_reflns_used    9895
_cell_measurement_temperature    100
_cell_measurement_theta_max      68.48
_cell_measurement_theta_min      4.24
_cell_volume                     884.06(5)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'Bruker CMOS area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0264
_diffrn_reflns_av_unetI/netI     0.0203
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            15418
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.476
_diffrn_reflns_theta_min         4.471
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.619
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.7052
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0750 before and 0.0447 after correction.
The Ratio of minimum to maximum transmission is 0.9364.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.313
_exptl_crystal_description       block
_exptl_crystal_F_000             368
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.23
_refine_diff_density_max         0.184
_refine_diff_density_min         -0.141
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;
 Flack x determined using 1478 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(6)
_refine_ls_extinction_coef       0.031(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     246
_refine_ls_number_reflns         3227
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0253
_refine_ls_R_factor_gt           0.0251
_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^)+(0.0360P)^2^+0.1437P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0642
_refine_ls_wR_factor_ref         0.0644
_reflns_Friedel_coverage         0.875
_reflns_Friedel_fraction_full    0.984
_reflns_Friedel_fraction_max     0.982
_reflns_number_gt                3197
_reflns_number_total             3227
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc03409c2.cif
_cod_data_source_block           cxy1738_0m
_cod_depositor_comments          'Adding full bibliography for 1567817.cif.'
_cod_database_code               1567817
_shelx_shelxl_version_number     2018/3
_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 Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B)
2.b Aromatic/amide H refined with riding coordinates:
 C13(H13), C24(H24), C7(H7), C9(H9), C12(H12), C23(H23), C21(H21), C17(H17),
 C6(H6), C5(H5), C14(H14), C22(H22), C15(H15), C16(H16)
2.c Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C)
;
_shelx_res_checksum              78259
_shelx_hkl_checksum              67816
_olex2_submission_special_instructions 'No special instructions were received'