Ni-Catalyzed Regioselective β,δ-Diarylation of Unactivated Olefins in Ketimines via Ligand-Enabled Contraction of Transient Nickellacycles: Rapid Access to Remotely Diarylated Ketones.
Basnet, Prakash; Dhungana, Roshan K.; Thapa, Surendra; Shrestha, Bijay; Kc, Shekhar; Sears, Jeremiah M.; Giri, Ramesh; Journal of the American Chemical Society 140 (2018) 7782–7786; doi:10.1021/jacs.8b03163

data_4132365
_publ_section_title
;
 Ni-Catalyzed Regioselective \b,\d-Diarylation of Unactivated Olefins in
 Ketimines via Ligand-Enabled Contraction of Transient Nickellacycles:
 Rapid Access to Remotely Diarylated Ketones.
;
_journal_issue                   25
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              7782
_journal_page_last               7786
_journal_paper_doi               10.1021/jacs.8b03163
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C24 H23 F6 O2'
_chemical_formula_sum            'C24 H23 F6 O2'
_chemical_formula_weight         457.42
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-12-04
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.5667(13)
_cell_length_b                   9.7395(11)
_cell_length_c                   23.460(3)
_cell_measurement_reflns_used    519
_cell_measurement_temperature    99(2)
_cell_measurement_theta_max      26.48
_cell_measurement_theta_min      3.34
_cell_volume                     2185.9(5)
_computing_cell_refinement       'SAINT V8.35A (?, 2016)'
_computing_data_collection       'Bruker APEX3'
_computing_data_reduction        'SAINT V8.35A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      99.51
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1580
_diffrn_reflns_av_unetI/netI     0.2701
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            10554
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.344
_diffrn_reflns_theta_min         2.264
_diffrn_source                   'fine--focus tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.122
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6006
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0874 before and 0.0770 after correction.
The Ratio of minimum to maximum transmission is 0.8057.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.390
_exptl_crystal_description       plate
_exptl_crystal_F_000             948
_exptl_crystal_size_max          0.228
_exptl_crystal_size_mid          0.157
_exptl_crystal_size_min          0.112
_refine_diff_density_max         0.595
_refine_diff_density_min         -0.304
_refine_diff_density_rms         0.072
_refine_ls_abs_structure_details
;
 Flack x determined using 449 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -1.4(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.977
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     284
_refine_ls_number_reflns         3994
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.977
_refine_ls_R_factor_all          0.2225
_refine_ls_R_factor_gt           0.0892
_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^)+(0.0518P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1357
_refine_ls_wR_factor_ref         0.1751
_reflns_Friedel_coverage         0.741
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                1802
_reflns_number_total             3994
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b03163_si_002.cif
_cod_data_source_block           jsop212121_a
_cod_database_code               4132365
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.987
_shelx_estimated_absorpt_t_min   0.973
_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
Uanis(C7) = Uanis(C3)
3.a Ternary CH refined with riding coordinates:
 C1(H1)
3.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B), C16(H16A,
 H16B), C17(H17A,H17B)
3.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C7(H7), C19(H19), C20(H20), C22(H22), C23(H23)
3.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C)
;
_shelx_res_checksum              71701
_shelx_hkl_checksum              28214
_olex2_submission_special_instructions 'No special instructions were received'