Mechanistic Investigation of Enantioconvergent Kumada Reactions of Racemic α-Bromoketones Catalyzed by a Nickel/Bis(oxazoline) Complex.
Yin, Haolin; Fu, Gregory C.; Journal of the American Chemical Society 141 (2019) 15433–15440; doi:10.1021/jacs.9b08185

data_4128989
_publ_section_title
;
 Mechanistic Investigation of Enantioconvergent Kumada Reactions of
 Racemic \a-Bromoketones Catalyzed by a Nickel/Bis(oxazoline) Complex.
;
_journal_issue                   38
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              15433
_journal_page_last               15440
_journal_paper_doi               10.1021/jacs.9b08185
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C51 H43 Br N2 Ni O2, C4 H8 O'
_chemical_formula_sum            'C55 H51 Br N2 Ni O3'
_chemical_formula_weight         926.60
_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     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-04-27
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   9.7540(5)
_cell_length_b                   17.1117(16)
_cell_length_c                   26.830(3)
_cell_measurement_reflns_used    9778
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      72.331
_cell_measurement_theta_min      3.062
_cell_volume                     4478.1(7)
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0475
_diffrn_reflns_av_unetI/netI     0.0415
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            32200
_diffrn_reflns_theta_full        72.77
_diffrn_reflns_theta_max         72.77
_diffrn_reflns_theta_min         3.06
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.036
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.6315
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0893 before and 0.0729 after correction.
The Ratio of minimum to maximum transmission is 0.8380.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.374
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       chip
_exptl_crystal_F_000             1928
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.552
_refine_diff_density_min         -0.603
_refine_diff_density_rms         0.081
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.00(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     562
_refine_ls_number_reflns         8614
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0501
_refine_ls_R_factor_gt           0.0452
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0520P)^2^+7.8010P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1112
_refine_ls_wR_factor_ref         0.1144
_reflns_number_gt                7993
_reflns_number_total             8614
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja9b08185_si_002.cif
_cod_data_source_block           NiPhBr
_cod_depositor_comments
;
The following automatic conversions were performed:

data name '_atom_site_symetry_multiplicity' was replaced with
'_atom_site_symmetry_multiplicity' as specified in the replacement
file
'/home/data/users/saulius/crontab/automatic-downloads/current/ACS/lib/lists/replacement-tags.lst'.

Automatic conversion script
Id: cif_correct_tags 6909 2019-04-08 15:41:33Z antanas 
;
_cod_original_cell_volume        4478.2(7)
_cod_database_code               4128989
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.943(17) 0.057(17)
2. 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
3.a Ternary CH refined with riding coordinates:
 C9(H9), C33(H33)
3.b Secondary CH2 refined with riding coordinates:
 C52(H52A,H52B), C53(H53A,H53B), C54(H54A,H54B), C55(H55A,H55B)
3.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C11(H11), C12(H12), C13(H13),
 C14(H14), C15(H15), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C23(H23),
  C24(H24), C25(H25), C26(H26), C27(H27), C35(H35), C36(H36), C37(H37),
 C38(H38), C39(H39), C41(H41), C42(H42), C43(H43), C44(H44), C45(H45), C47(H47),
  C48(H48), C49(H49), C50(H50), C51(H51)
3.d Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C30(H30A,H30B,H30C)
;
_olex2_date_sample_data_collection 2017-04-26
_olex2_date_sample_submission    2017-04-22
_olex2_submission_original_sample_id HLY-I-252
_olex2_submission_special_instructions 'No special instructions were received'