Enantioselective Synthesis of Atropisomeric Anilides via Pd(II)-Catalyzed Asymmetric C-H Olefination.
Yao, Qi-Jun; Xie, Pei-Pei; Wu, Yong-Jie; Feng, Ya-Lan; Teng, Ming-Ya; Hong, Xin; Shi, Bing-Feng; Journal of the American Chemical Society 142 (2020) 18266–18276; doi:10.1021/jacs.0c09400

data_4135280
_publ_section_title
;
 Enantioselective Synthesis of Atropisomeric Anilides via Pd(II)-Catalyzed
 Asymmetric C-H Olefination.
;
_journal_issue                   42
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              18266
_journal_page_last               18276
_journal_paper_doi               10.1021/jacs.0c09400
_journal_volume                  142
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         '0.5(C H2 Cl2), C34 H28 F6 N2 O3'
_chemical_formula_sum            'C34.5 H29 Cl F6 N2 O3'
_chemical_formula_weight         669.04
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-05-21
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                71.8740(10)
_cell_angle_beta                 85.8650(10)
_cell_angle_gamma                84.0380(10)
_cell_formula_units_Z            2
_cell_length_a                   8.9752(3)
_cell_length_b                   12.9775(4)
_cell_length_c                   14.8463(5)
_cell_measurement_reflns_used    9626
_cell_measurement_temperature    170(2)
_cell_measurement_theta_max      72.21
_cell_measurement_theta_min      3.98
_cell_volume                     1633.08(9)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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      170.0
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.988
_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  0.0435
_diffrn_reflns_av_unetI/netI     0.0548
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            31024
_diffrn_reflns_point_group_measured_fraction_full 0.949
_diffrn_reflns_point_group_measured_fraction_max 0.935
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.458
_diffrn_reflns_theta_min         3.135
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.666
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.4804
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1345 before and 0.0765 after correction.
The Ratio of minimum to maximum transmission is 0.6375.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.361
_exptl_crystal_description       needle
_exptl_crystal_F_000             690
_exptl_crystal_size_max          0.704
_exptl_crystal_size_mid          0.295
_exptl_crystal_size_min          0.206
_refine_diff_density_max         0.591
_refine_diff_density_min         -0.524
_refine_diff_density_rms         0.057
_refine_ls_abs_structure_details
;
 Flack x determined using 5455 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.096(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     844
_refine_ls_number_reflns         12075
_refine_ls_number_restraints     39
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0555
_refine_ls_R_factor_gt           0.0551
_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^)+(0.1035P)^2^+0.4641P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1508
_refine_ls_wR_factor_ref         0.1514
_reflns_Friedel_coverage         0.892
_reflns_Friedel_fraction_full    0.904
_reflns_Friedel_fraction_max     0.881
_reflns_number_gt                11906
_reflns_number_total             12075
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c09400_si_002.cif
_cod_data_source_block           190520_yqj_h_097_5_0m
_cod_depositor_comments
;
Adding full bibliography for 4135280--4135281.cif.

2025-07-29
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_moiety     'C H2 Cl2, 2(C34 H28 F6 N2 O3)'
_cod_original_formula_sum        'C69 H58 Cl2 F12 N4 O6'
_cod_original_formula_units_Z    1
_cod_original_formula_weight     1338.09
_cod_database_code               4135280
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.725
_shelx_estimated_absorpt_t_min   0.387
_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. Uiso/Uaniso restraints and constraints
C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim C61: within 1.7A with sigma
of 0.01 and sigma for terminal atoms of 0.02
3.a Ternary CH refined with riding coordinates:
 C32(H32), C66(H66)
3.b Secondary CH2 refined with riding coordinates:
 C69(H69A,H69B), C21(H21A,H21B), C55(H55A,H55B)
3.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C5(H5), C8(H8), C9(H9), C11(H11), C15(H15), C16(H16),
 C17(H17), C23(H23), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28), C29(H29),
  C35(H35), C37(H37), C39(H39), C42(H42), C43(H43), C45(H45), C49(H49),
 C50(H50), C51(H51), C57(H57), C58(H58), C59(H59), C60(H60), C61(H61), C62(H62),
  C63(H63)
3.d Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C65(H65A,H65B,
 H65C), C67(H67A,H67B,H67C), C68(H68A,H68B,H68C)
;
_shelx_res_checksum              32764
_shelx_hkl_checksum              33262
_olex2_submission_special_instructions 'No special instructions were received'