Diverting C–H Annulation Pathways: Nickel-Catalyzed Dehydrogenative Homologation of Aromatic Amides
He, Zhiqi; Huang, Yong; ACS Catalysis 6 (2016) 7814–; doi:10.1021/acscatal.6b02477

data_4516717
_publ_section_title
;
 Diverting C--H Annulation Pathways: Nickel-Catalyzed Dehydrogenative
 Homologation of Aromatic Amides
;
_journal_issue                   11
_journal_name_full               'ACS Catalysis'
_journal_page_first              7814
_journal_paper_doi               10.1021/acscatal.6b02477
_journal_volume                  6
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C44 H26 F4 N2 O, C H3 O'
_chemical_formula_sum            'C45 H29 F4 N2 O2'
_chemical_formula_weight         705.70
_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
_audit_creation_date             2015-02-10
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2014.11.28 svn.r3106 for OlexSys, GUI svn.r4959)
;
_cell_angle_alpha                90
_cell_angle_beta                 122.222(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   29.3161(7)
_cell_length_b                   8.8470(3)
_cell_length_c                   16.2475(11)
_cell_measurement_reflns_used    0.89
_cell_measurement_temperature    566(2)
_cell_measurement_theta_max      0.854
_cell_measurement_theta_min      0.850
_cell_volume                     3564.9(5)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_diffrn_ambient_temperature      566.3
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0406
_diffrn_reflns_av_unetI/netI     0.0413
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -35
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            21289
_diffrn_reflns_point_group_measured_fraction_full 0.928
_diffrn_reflns_point_group_measured_fraction_max 0.925
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.208
_diffrn_reflns_theta_min         6.589
_exptl_absorpt_coefficient_mu    0.787
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.315
_exptl_crystal_description       block
_exptl_crystal_F_000             1460
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.408
_refine_diff_density_min         -0.154
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 1992 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.01(8)
_refine_ls_extinction_coef       0.0018(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   1.080
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     480
_refine_ls_number_reflns         6041
_refine_ls_number_restraints     146
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.0537
_refine_ls_R_factor_gt           0.0472
_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^)+(0.0917P)^2^+0.4026P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1342
_refine_ls_wR_factor_ref         0.1435
_reflns_Friedel_coverage         0.740
_reflns_Friedel_fraction_full    0.852
_reflns_Friedel_fraction_max     0.847
_reflns_number_gt                5210
_reflns_number_total             6041
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs6b02477_si_002.cif
_cod_data_source_block           1111
_cod_original_cell_volume        3564.9(4)
_cod_database_code               4516717
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.859
_shelx_estimated_absorpt_t_min   0.859
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C55-O54
 1.54 with sigma of 0.02
 O54-O54_$1
 1.54 with sigma of 0.02
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), N4(H4), C15(H15), C16(H16), C17(H17), C18(H18), C21(H21),
 C22(H22), C24(H24), C25(H25), C28(H28), C29(H29), C31(H31), C32(H32), C33(H33),
  C34(H34), C35(H35), C36(H36), C37(H37), C38(H38), C40(H40), C42(H42),
 C43(H43), C45(H45), C46(H46)
4.b Idealised Me refined as rotating group:
 C55(H55A,H55B,H55C)
;
_olex2_submission_special_instructions 'No special instructions were received'