Enantioselective Assembly of Cycloenones with a Nitrile-Containing All-Carbon Quaternary Center from Malononitriles Enabled by Ni Catalysis.
Lu, Zhiwu; Hu, Xu-Dong; Zhang, Hui; Zhang, Xiao-Wen; Cai, Jinhui; Usman, Muhammad; Cong, Hengjiang; Liu, Wen-Bo; Journal of the American Chemical Society 142 (2020) 7328–7333; doi:10.1021/jacs.0c02075

data_4134699
_publ_section_title
;
 Enantioselective Assembly of Cycloenones with a Nitrile-Containing
 All-Carbon Quaternary Center from Malononitriles Enabled by Ni Catalysis.
;
_journal_issue                   16
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              7328
_journal_page_last               7333
_journal_paper_doi               10.1021/jacs.0c02075
_journal_volume                  142
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C26 H20 Br N O'
_chemical_formula_sum            'C26 H20 Br N O'
_chemical_formula_weight         442.34
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-08-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.136(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.866(2)
_cell_length_b                   6.6629(6)
_cell_length_c                   13.5743(11)
_cell_measurement_reflns_used    9989
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      65.34
_cell_measurement_theta_min      3.26
_cell_volume                     2152.9(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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      296.15
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0393
_diffrn_reflns_av_unetI/netI     0.0432
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            12461
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        65.335
_diffrn_reflns_theta_max         65.335
_diffrn_reflns_theta_min         3.264
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.718
_exptl_absorpt_correction_T_max  0.7526
_exptl_absorpt_correction_T_min  0.3418
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1764 before and 0.0703 after correction.
The Ratio of minimum to maximum transmission is 0.4542.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.365
_exptl_crystal_description       block
_exptl_crystal_F_000             904
_refine_diff_density_max         0.283
_refine_diff_density_min         -0.303
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Flack x determined using 1492 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.059(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     262
_refine_ls_number_reflns         3628
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0331
_refine_ls_R_factor_gt           0.0324
_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^)+(0.0454P)^2^+0.6387P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0863
_refine_ls_wR_factor_ref         0.0874
_reflns_Friedel_coverage         0.800
_reflns_Friedel_fraction_full    0.965
_reflns_Friedel_fraction_max     0.965
_reflns_number_gt                3537
_reflns_number_total             3628
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c02075_si_003.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 4134698--4134699.cif.'
_cod_database_code               4134699
_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
2.a Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C16(H16A,H16B), C20(H20A,H20B)
2.b Aromatic/amide H refined with riding coordinates:
 C26(H26), C14(H14), C25(H25), C5(H5), C22(H22), C3(H3), C23(H23), C13(H13),
 C12(H12), C10(H10), C2(H2), C11(H11), C4(H4), C1(H1)
;
_shelx_res_checksum              92860
_shelx_hkl_checksum              90293
_olex2_submission_special_instructions 'No special instructions were received'